Separators, batteries, systems, and methods for idle start stop vehicles

ABSTRACT

In accordance with at least selected embodiments or aspects, the present invention is directed to improved, unique, and/or high performance ISS lead acid battery separators, such as improved ISS flooded lead acid battery separators, ISS batteries including such separators, methods of production, and/or methods of use. The preferred ISS separator may include negative cross ribs and/or PIMS minerals. In accordance with more particular embodiments or examples, a PIMS mineral (preferably fish meal, a bio-mineral) is provided as at least a partial substitution for the silica filler component in a silica filled lead acid battery separator (preferably a polyethylene/silica separator formulation). In accordance with at least selected embodiments, the present invention is directed to new or improved batteries, separators, components, and/or compositions having heavy metal removal capabilities and/or methods of manufacture and/or methods of use thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application claiming the benefit of andpriority from U.S. application Ser. No. 17/463,116, filed on Aug. 31,2021; which claims priority to U.S. application Ser. No. 16/142,158,filed Sep. 26, 2018, now U.S. Pat. No. 11,104,804 issued on Aug. 31,2021; which claims priority to U.S. application Ser. No. 13/239,483filed Sep. 22, 2011, now U.S. Pat. No. 10,119,025, issued on Nov. 6,2018, and which claims priority to and the benefit of U.S. provisionalpatent applications Ser. No. 61/385,285, filed Sep. 22, 2010, and Ser.No. 61/532,598, filed Sep. 9, 2011, all of which are hereby fullyincorporated by reference herein.

FIELD OF THE INVENTION

In accordance with at least selected embodiments, the present inventionis directed to new or improved battery separators, batteries, systems,components, compositions, and/or methods of manufacture and/or methodsof use. In accordance with at least selected embodiments, examples oraspects, the present invention is directed to new, improved, unique,and/or complex performance battery separators, lead acid batteryseparators, flooded lead acid battery separators, enhanced flooded leadacid battery separators, ISS or micro-hybrid battery separators, ISSflooded lead acid battery separators, ISS enhanced flooded lead acidbattery separators, batteries including such separators, systems orvehicles including such batteries or separators, and/or methods ofproduction, and/or methods of use.

BACKGROUND

In order to reduce fuel consumption and generation of tail pipeemissions, auto manufacturers have implemented varying degrees ofelectrical hybridization. (See FIG. 1) One form Hybrid Electric Vehicle(HEV) is often referred as the ‘Micro HEV’. In such Micro HEV orconcepts, the automobile has the idle stop/start (ISS) function andoften regenerative braking. In order to keep costs down, many automanufacturers are considering a flooded lead acid battery to meet theelectrical functionality associated with the ISS function. As thefunctionality associated with this battery is often different than astandard automotive application, such as Starting Lighting and Ignition(SLI) battery, this may result in different functions or preferredperformance of the ISS battery separator (and ISS battery).

The ISS flooded lead acid battery will be operated in a partial state ofcharge (PSoC), approximately 50 to 80% unlike the typical SLI batterywhich is usually operated at 100% state of charge. With regenerativebraking and frequent restarting, the battery will experience shallowcharge and recharge cycles. Depending on the design of the electricalsystem, the ISS battery may not normally go into overcharge and thus maynot generate oxygen and hydrogen gas which can be useful for acidmixing.

Although the ISS battery of choice may be an ISS or enhanced floodedlead acid battery, it is understood that the ISS battery may be a gel,polymer or other battery, a capacitor, a super capacitor, anaccumulator, a battery/capacitor combination, and/or the like.

The advent of Micro HEV and ISS with or without regenerative breakingsets new demands on the battery and the battery separator. Hence, a needexists for new or improved battery separators, batteries, systems,components, compositions, and/or methods of manufacture and/or methodsof use; new, improved, unique, and/or complex performance batteryseparators, lead acid battery separators, flooded lead acid batteryseparators, enhanced flooded lead acid battery separators, ISS ormicro-hybrid battery separators, ISS flooded lead acid batteryseparators, ISS enhanced flooded lead acid battery separators, batteriesincluding such separators, systems or vehicles including such batteriesor separators, and/or methods of production, and/or methods of use;and/or the like.

A group of inorganic (mineral) compounds are known to effectively bindheavy metals such as lead, cadmium, iron, zinc, and copper. Themechanism by which the minerals bind heavy metals is termed “PhosphateInduced Metal Stabilization” (PIMS) and is widely utilized for theenvironmental remediation of heavy metals from contaminated soils andwater. In environmental remediation applications, bulk quantities ofminerals possessing PIMS affinity for toxic metals are mixed withcontaminated soil or contained within a housing whereby contaminatedwater may perfuse through the bulk PIMS mineral cake to reduce heavymetal contamination.

A common failure mode within the lead-acid (or lead-calcium) batteryindustry is the phenomenon of “hydration shorts”. This type of shortcircuit is typically formed in batteries when they are allowed to stayat very low acid concentrations (low charge) for an extended period oftime. In a charged state, the acid density is high (for example, 1.28g/cm³) and the solubility of lead sulfate is low. At low charge, theacid density decreases and the solubility of lead sulfate increases. Atlow charge, lead sulfate (PbSO₄), from the electrode plates, enters intothe electrolyte solution (sulfuric acid H₂SO₄). Upon recharging, leadsulfate is precipitated and can form a layer on the bottom of many ofthe separator pores (the separator pores are large compared to the ionicradii of lead and sulfate). Upon additional recharging of the batteryand contact with the negative electrode of the battery, the precipitatedlead sulfate can be reduced to lead and thousands of microshorts betweenthe electrodes can be generated (hydration shorts and battery failure).

Typically, this “hydration shorts” phenomenon occurs when a batteryencounters a slow discharge as in the case of storage over extendedperiods without maintenance of charge. The conventional approach to theprevention of hydration shorts consists of addition of sodium sulfate(Na₂SO₄) to the electrolyte solution during battery manufacture. Thisapproach requires an additional manufacturing step, the addition ofsodium sulfate to the electrolyte, and adds complexity to the batteryprocessing. Sodium sulfate addition acts to “hinder” hydration shortsvia the Common Ion Effect but does not address the root cause (solublelead generation).

As such, there exists a need for new or improved battery separators andthe like for particular battery applications, particular uses, and/orfor addressing, reducing or eliminating the phenomenon of “hydrationshorts” in lead acid batteries.

SUMMARY

In accordance with at least selected embodiments, the present inventionaddresses, provides or is directed to the above needs for new orimproved battery separators, batteries, systems, components,compositions, and/or methods of manufacture and/or methods of use; new,improved, unique, and/or complex performance battery separators, leadacid battery separators, flooded lead acid battery separators, enhancedflooded lead acid battery separators, ISS or micro-hybrid batteryseparators, ISS flooded lead acid battery separators, ISS enhancedflooded lead acid battery separators, batteries including suchseparators, systems or vehicles including such batteries or separators,and/or methods of production, and/or methods of use; and/or the like.

Although the preferred battery embodiment of the present invention maybe an ISS flooded lead acid battery, it is understood that the presentbattery may be a gel, polymer or other battery, a capacitor, a supercapacitor, an accumulator, a battery/capacitor combination, and/or thelike.

Also, although the preferred improved separators of the presentinvention may find special applicability in ISS batteries, they may alsobe used in other batteries or devices.

The advent of Micro HEV and ISS with or without regenerative breakingsets new demands on the battery and the battery separator. (See FIG. 2)Such new demands may be addressed or met by at least certain embodimentsof the batteries or separators of the present invention.

The ISS flooded lead acid battery will be operated in a partial state ofcharge (PSoC), approximately 50 to 80% unlike the typical SLI batterywhich is usually operated at 100% state of charge. With regenerativebraking and frequent restarting, the battery will experience shallowcharge and recharge cycles. Depending on the design of the electricalsystem, the ISS battery may not normally go into overcharge and thus maynot generate oxygen and hydrogen gas which can be useful for acidmixing.

In accordance with at least selected embodiments, examples or aspects ofthe present invention, the new demands described above, may preferablylead to the following specific possibly preferred changes to theseparator, battery and/or electrical system:

1) Charge Acceptance/Power Delivery—The lead-acid battery is anexcellent storage medium for energy, but one of the limitations is theability to accept charge rapidly, particularly when the battery is at ahigh state of charge. In ISS applications, this rapid charge may comefrom the use of regenerative braking, which will recover much of theenergy used in slowing the vehicle. For this reason, the battery willtypically be operated at a lower state of charge. The battery separatormust also contribute to the ability of the battery to accept chargerapidly. Below are some specific preferred changes to the separator tohelp increase charge acceptance/power delivery.

-   -   a. Low Electrical Resistance (ER)—In order to maximize charge        acceptance during regenerative braking and power delivery during        restart of the internal combustion engine, it may be important        to minimize the separator ER. The separator ER can be lowered        via the following methods:        -   i. Lower Back-Web (BW) Thickness—As the BW thickness is the            main contributor to separator ER, this can be reduced from            typical values which range from 150 to 250 micron. However            as this is done, the material may become very challenging to            process on typical envelopers. Here it is recommended to            lower the BW thickness between 75 to 150 microns and then            reinforce the transversal stiffness with the use of negative            cross ribs. (See FIGS. 5 and 6)        -   ii. Increase silica to polymer ratio—A second method to            reduce ER in the separator is to increase the loading of            silica, relative to the polymer content. One possibly            significant issue with this change is that the oxidation            resistance of the separator may be compromised to some            degree. In a standard SLI battery, the battery is subjected            to heavy overcharging, wherein oxidizing species are            generated in the positive plate. However, in ISS            applications, the battery will not be generating oxidizing            species as overcharge situations will be limited by design            of the electrical system, therefore the separator will not            be required to have as much oxidation resistance as is            required in a typical SLI application. The silica to polymer            ratio could vary from about 3.0/1.0 to 5.0/1.0.        -   iii. Utilize High Oil Absorption silica—A third approach to            reduce the ER is to utilize a silica with a high surface            area (e.g. >200 g/m2), which typically yields a high oil            absorption. With this type of silica, the amount of pore            forming agent can be increased from 60 to 65% by weight to            70 to 80% in the extrusion process and thus yields a            significantly higher final porosity and lower electrical            resistance. (See FIG. 11)    -   b. Minimize Gas Entrapment—It has been recognized that hydrogen        and oxygen gas generated by the battery active materials during        charge and discharge may become trapped by the separator,        insulating a portion of the plate and rendering it unable to        partake in charge and discharge reactions. This may ultimately        limit the ability of the battery to accept charge and deliver        power. Following are some specific changes to reduce the        opportunity for gas entrapment:        -   i. Laminate Structure—In a number of the designs that have            been proposed for ISS batteries, a laminate structure has            been incorporated into the separator in order to help retain            the positive active material (PAM) in the positive plate. In            general, these laminates tend to increase the amount of gas            entrapped in the cell. (See FIGS. 12 and 13) By modifying            the laminate structure, it is anticipated that gas            entrapment could be reduced significantly. Potential            preferred modifications could be:            -   1. Treatment of the laminate with a chemical or plasma                to modify surface energy to shed gas bubbles            -   2. Perforation to allow bubbles an area to coagulate and                escape the laminate matrix            -   3. Addition of nucleating agents            -   4. Changing the structure of the laminate during                formation            -   5. Addition of polymer fibers to the laminate structure            -   6. Addition of wetting agents            -   7. Change the orientation on the fiber structure of the                laminate so gas bubbles are less likely to attach to the                structure.            -   8. Minimize the thickness of the structure so that there                are simply less sites for bubble adhesion.        -   ii. Wetting Agent Selection—It has been demonstrated that            the selection of a wetting agent for use on the polyethylene            separator can have a significant influence on the retention            of gas bubbles in the cell. It is understood that wetting            agents with more hydrophobic behavior may exhibit better            performance in this aspect than those that tend to be            hydrophilic. For example, ethoxylated fatty alcohols are            generally preferred over substituted sulfosuccinates.        -   iii. Cross-Ribs (Negative and/or Positive)—In testing            performed to examine gassing behavior, it has been noted            that small negative cross ribs appear to assist in the            nucleation and/or transport of gas bubbles to the outside of            the cell, allowing the gas to escape from between the            plates, reducing the potential for gas entrapment.        -   iv. Nucleation of Gas—A wide variety of modifications may be            made to the separator in order to assist in the providing            areas on the separator to act as nucleation sites for gas            bubbles to quickly and efficiently grow to the point where            they are released from the separator and travel out of the            area between the plates.            -   1. Shape—By incorporating certain nanostructures onto                the surface of the polyethylene separator, gas                nucleation may be increased significantly. These                nanostructures may take the form of pyramids, chevrons,                or pillars, as examples. They may be formed by                calendaring, laser ablation or controlled chemical                oxidation.            -   2. Additives—Additives may be incorporated into the                matrix of the separator in order to provide areas on the                surface where they change the surface structure or                energy. These changes will encourage the nucleation of                small gas bubbles generated to a critical volume.                Examples of these additives are carbon fibers, carbon                nanotubes, or barium sulfate.

2) Hydration Shorts—This type of short circuit is formed in batterieswhen they are allowed to stay at very low acid concentrations for anextended period of time. This phenomenon is well known in the batteryindustry, as is the use of sodium sulfate in the electrolyte as apotential remedy for this phenomenon. In an ISS application, where thebattery seldom receives a full charge, the danger of forming hydrationshorts is believed to be significantly greater than in a typical SLIbattery. The following are some of the significant separator changesthat may help reduce the occurrence of hydration shorts:

-   -   a. Common Ion Effect—It is well known that the addition of        sodium sulfate to the battery electrolyte will inhibit the        formation of hydration shorts, via the Common Ion Effect. In the        present variant, sodium sulfate is incorporated into the        separator matrix (and/or laminate), allowing the sodium sulfate        to be in the proper location to most efficiently reduce the        chance of formation of hydration shorts.    -   b. Heavy Metal Sequestration—By irreversibly adsorbing and        sequestering lead ions that are in solution, certain additives        could be incorporated into the separator to inhibit hydration        short formation. Examples of materials that may be used for this        include apatite, zeolites, lignins and rubber-derivatives.    -   c. Location of Additives—It should be noted that the additives        associated with the Common Ion Effect or the Sequestration of        heavy metals can be added directly to the matrix of the        separator, coated or contained on laminate structure or coated        onto the container of the battery case either before or after        the injection molding process, and/or the like.    -   d. Lower Acid Displacement—If the separator were capable of        displacing less acid, then the total amount of sulfate ions in        the acid solution would be higher, resulting in a retardation of        the hydration effect. In other words, this would be an        additional buffer against the over-discharge of the battery. In        order to accomplish this, potential preferred separator        modifications may include lower backweb thickness (as discussed        previously), higher porosity, or less rib mass of the separator.        -   i. Serrated/Battlement Ribs—A serrated or battlement rib            design may be used to remove mass from the ribs. This            concept is detailed in U.S. Pat. No. 7,094,498 hereby            incorporated by reference. By modifying the rib design in            this way, the separator will have less acid displacement.

3) Improve Cycle Life—In order to meet the expectations of both thebattery and vehicle manufacturers, the cycle life of a typical lead acidbattery should be improved, particularly when the battery is subjectedto high temperatures and a heavy cycling duty. One school of thought isto reduce the state of charge of the battery to reduce the amount ofovercharge and subsequent corrosion of the positive plate. However, byfollowing this route, the chance of having hydration shorts increasesdramatically. By modifying the separator, these potential issues may beeliminated. A few of the potential preferred modifications are detailedbelow.

-   -   a. Laminate—In many deep cycle lead-acid batteries, laminates        are utilized to retain the positive active mass in the positive        grid. This structure eventually incorporated into the positive        plate due to the natural expansion of the positive active mass        during cycling operation. This allows the positive active mass        to maintain intimate contact, and therefore capacity for a        significantly longer period of time than otherwise possible. It        is anticipated that separators for flooded ISS applications will        incorporate a laminate, as the anticipated duty cycle and        environment will be harsh.        -   i. Glass Mat—In many flooded lead-acid batteries, glass mats            are utilized in order to help retain intimate contact            between the positive active material and the positive grid.            One potential variant envisioned for ISS will continue to            utilize glass mats, albeit with the potential to mix            different fiber lengths and widths in the mats ranging in            compressed thickness from 0.1 mm to 1.0 mm.        -   ii. Synthetic Nonwovens—Nonwoven polymeric mats have also            been utilized recently as active material retainers in            lead-acid batteries. These materials are typically made of            polyester. (refer to Polymat published patent application,            US 2006/0141350 A1, hereby incorporated by reference herein)        -   iii. Hybrid—It is imagined that hybrids of glass mixed with            polymers may be incorporated into a hybrid mat, which will            have the rigidity and oxidation resistance inherent in the            glass with the tear resistance and toughness of nonwovens.            By combining the properties of both materials, a mat with            superior properties for the battery may be produced.    -   b. Profile Selection—The selection of a profile or ribbing        design is not often considered for adding benefits to a typical        flooded lead-acid battery. For ISS applications, however, it is        believed that the profile design may have a much greater impact        on the battery performance. The goal of having lower acid        displacement may be contributed to by the profile design. (See        FIG. 26) Conversely, it is established within the industry that        tighter rib spacing is beneficial for deep cycle applications. A        unique compromise between the two may be required.

4) Acid Stratification—In a variety of flooded lead-acid batteries, thestratification of acid in the electrolyte has been an issue inapplications with heavy cycling requirements and few complete recharges.When a battery cycles repeatedly, but is not fully charged, orovercharged, the acid in the battery can separate, to the point wherethere will be water at the top of the battery, and concentrated sulfuricacid at the bottom. Typically, battery manufacturers will specify that abattery should be overcharged to some degree, promoting the electrolysisof water. The hydrogen and oxygen produced during this overcharging willagitate the electrolyte, mixing the water and acid. As mentionedearlier, in ISS applications, batteries will be maintained in PSoCconditions with few opportunities for overcharging to mix the acid.Therefore, any potential benefits to either acid mixing or retardationof acid stratification from the separator will be critical.

-   -   a. Profile Selection—As mentioned earlier, profile selection        will be a critical attribute for a number of properties. Another        benefit may come from the incorporation of horizontal ribs        across the surface of the separator in acting as a physical        barrier to acid stratification. It is imagined that these        cross-ribs could take a wide range of forms (reference the above        mentioned negative cross-rib patent application and positive        cross-rib patent).    -   b. Laminate Structure—The laminate structure attached to the        polyethylene separator may also serve to discourage acid        stratification. By aligning the fibers in a certain pattern        across and through the material, it is envisioned that the glass        mat may help to keep the acid from become stratified.    -   c. Surface Area—Minimizing the acid stratification may also be        accomplished by increasing the surface area of the separator        structure. This can be accomplished by first decreasing the        fiber diameter of the laminate structure or second by increasing        the internal surface of the separator by the type or        concentration of silica.

5) VRLA—It is also recognized that valve-regulated lead acid (VRLA)batteries may have a role in the market for automotive ISS applications.In this type of construction, the electrolyte is absorbed and held inthe matrix of the separator. Predominant technologies for this are usingan absorptive glass mat (AGM) separator, or gelling the electrolyte,typically with silica as the binding agent. A few novel approaches toVRLA technology are reviewed below in some detail.

-   -   a. Acid Jellifying Separator—The acid jellifying separator (AJS)        is a concept that has been utilized in the past. By modifying        the separator to incorporate high surface area silica with a        high loading of such silica in the polyethylene separator, a new        or improved product has been produced that allows the separator        to absorb enough acid to make it a viable separator for a VRLA        design. This Daramic AJS product may allow a manufacturer to        utilize standard flooded battery construction equipment and        techniques to produce a VRLA product. The AJS separator will        have superior behavior in improving cycling, as it is in        intimate contact with the positive plate, preventing shedding of        the active material. It will also prevent acid stratification        issues, as the polymer matrix along with the silica will inhibit        the flow and separation of the electrolyte.    -   b. Polyethylene/Absorptive Glass Mat Hybrid—One of the key        limiting factors in reducing plate spacing in batteries with AGM        separators is the ability of AGM to hold up against plate        defects and prevent short circuits from occurring. Typically,        these short circuits do not show up until after the battery has        gone through the complete assembly and charging process, adding        to the high cost of this type of product. By incorporating a        flat PE separator membrane into or on one side of the AGM        separator, the plate spacing in the battery may be reduced        without increasing failures in early life. The PE separator will        act as a shield, reducing the possibility that minor plate        defects will cause a short circuit.    -   c. Other Laminate Hybrids—It is imagined that other laminate        systems, whether nonwovens or other glass mats could be utilized        in conjunction with a flat PE separator membrane to make an        acceptable VRLA separator.

The inventive lead-acid storage battery may be required not only tosupply power as a main power supply for electric cars, but also toprovide a new function as a power supply for starting and recoveringregenerative current for hybrid electric cars, simplified hybrid carsand ISS-compatible cars having an idle stop and start (ISS) function.

The complete description and drawings of separators with negative crossribs of various configurations and methods of U.S. patent applicationSer. No. 61/253,096, filed on Oct. 20, 2009, entitled “LEAD ACID BATTERYSEPARATORS WITH CROSS RIBS AND RELATED METHODS” and of pending U.S.patent application Ser. No. 12/904,371, filed on Oct. 14, 2010, entitled“BATTERY SEPARATORS WITH CROSS RIBS AND RELATED METHODS” are each herebyfully incorporated by reference herein.

In accordance with at least selected embodiments, the present inventionaddresses the need for new or improved battery separators and the likefor particular battery applications, particular uses, and/or foraddressing, reducing or eliminating the phenomenon of “hydration shorts”in lead acid batteries.

In accordance with at least selected embodiments, the present inventionaddresses, provides or is directed to new or improved batteries,separators, components, and/or compositions having heavy metal removalcapabilities and/or methods of manufacture and/or methods of usethereof; new or improved lead acid batteries, lead acid batteryseparators (single or multi-layer), lead acid battery components (suchas battery casings, battery parts, porous bags, laminates, coatings,surfaces, fillers, electrode formulations, electrolytes, and/or thelike) and/or polymer or resin compositions having heavy metal removalcapabilities and/or methods of manufacture and/or methods of usethereof; new or improved lead acid batteries, lead acid batteryseparators (single or multi-layer), lead acid battery components (suchas battery casings, battery parts, porous bags, laminates, coatings,surfaces, fillers, electrode formulations, electrolytes, and/or thelike) and/or polymer or resin compositions having heavy metal removalcapabilities and utilizing at least one PIMS mineral as at least onefiller component therein; a silica filled lead acid battery separatorwherein a PIMS mineral (preferably ground fish meal, a bio-mineral) isprovided as at least a partial substitution for the silica fillercomponent in the silica filled lead acid battery separator (preferably apolyethylene/silica separator formulation); and/or the like.

In accordance with at least selected embodiments, the present inventionaddresses, provides or is directed to new or improved batteries,separators, components (such as battery casings, battery parts, porousbags, laminates, coatings, surfaces, fillers, electrochemically activeelectrode formulations, electrolytes, and/or the like), and/orcompositions having heavy metal removal capabilities utilizing at leastone source of natural or synthetic hydroxyapatite having heavy metalbinding capabilities, such as a PIMS mineral, and/or methods ofmanufacture and/or methods of use thereof.

In accordance with at least selected possibly preferred embodiments ofthe present invention, a believed novel concept of utilizing PIMSminerals as a filler component within a microporous lead-acid batteryseparator is provided. In accordance with one particular possibly morepreferred embodiment or example, the PIMS mineral (preferably fish meal,a bio-mineral) is provided as at least a partial substitution for thesilica filler component in contemporary silica filled lead acid batteryseparator (preferably a polyolefin/silica or polyethylene/silica/oilseparator formulation).

In accordance with selected embodiments or aspects of the presentinvention, a variety of “Phosphate Induced Metal Stabilization” (PIMS)minerals have been identified; some of which have been evaluated forlead affinity. A PIMS mineral derived from fish bone (such ascommercial, lab ground fish meal) has been shown to have greatestaffinity for lead ion over the other samples evaluated. The fish bonepowder was extruded via pilot operation into a typical lead-acid batteryseparator format at several loading concentrations. The resulting PIMSincorporating separator was evaluated for lead removal efficiency; theseparator demonstrated substantial reduction of lead concentration inacidic solution. For example, % Pb reductions of about 17% to 100% weredemonstrated. In accordance with at least certain embodiments, it ispreferred that the fish bone powder be added to substitute for a portionof the silica filler at substitution levels of about 1% to 20% of thesilica, more preferably about 2% to 10%, and most preferably at about 2%to 5%. In accordance with at least other certain embodiments, it ispreferred that the ground fish bone powder (ground fish meal) be addedto substitute for a portion of the silica filler at substitution levelsof about 1% to 50% or more of the silica, more preferably about 5% to30%, and most preferably at about 10% to 20%.

It is believed that this is the first commercial use of a bio-mineral ina battery separator, in an extruded polyolefin polymer resin, and in aporous polymer film or membrane.

In accordance with at least selected embodiments, lead reduction isachieved by incorporating PIMS minerals in lead-acid battery separators,preferably incorporating PIMS mineral derived from fish bone.

The present invention represents a novel or improved microporousmembrane substrate with chemically active properties. A range of variouschemically active or reactive mineral fillers are available and amenableto the separator extrusion and extraction process. These minerals areavailable at low cost in desired purity and in the case of fish bone areindustrial by-products available from multiple sources. Advantagesinclude low cost of raw material as well as streamlining existingbattery production processes involving sodium sulfate.

The preferred separators of the present invention are microporousmaterials (e.g. pores less than 1 micron). Nonetheless, other materialssuch as porous or macroporous materials are contemplated. For example,macroporous separators (e.g. pores greater than 1 micron) would includeseparators made from rubber, PVC, synthetic wood pulp (SWP), glassfibers, cellulosic fibers, polypropylene, and combinations thereof.

In accordance with at least selected embodiments, the present inventionis directed to other components and/or compositions having heavy metalremoval capabilities and/or methods of manufacture and/or methods of usethereof. In accordance with at least certain possibly preferredembodiments, the present invention is directed to new or improved leadacid battery components (such as battery casings, battery parts, porousbags, laminates, coatings, surfaces, fillers, electrodes, electrolytes,and/or the like) and/or polymer or resin compositions having heavy metalremoval capabilities and/or methods of manufacture and/or methods of usethereof. In accordance with at least possibly more preferred particularembodiments, the present invention is directed to such new or improvedlead acid battery components (such as battery casings, battery parts,porous bags, laminates, coatings, surfaces, fillers, electrodes,electrode formulations, electrolytes, and/or the like) and/or polymer orresin compositions utilizing at least one PIMS mineral as at least onefiller component therein. In accordance with at least one particularembodiment, the PIMS mineral (preferably ground fish meal, abio-mineral) is provided as at least a partial substitution for thesilica filler component in a silica filled polymer composition, such asa polyolefin/silica composition, for example, in apolyethylene/silica/oil formulation suitable for slot die extrusion.

In accordance with at least certain other embodiments or examples, theinvention is directed to new or improved batteries, separators,components, and/or compositions having lead removal, binding, bonding,absorbing, retaining, and/or scavenging capabilities and/or methods ofmanufacture and/or methods of use thereof.

In accordance with at least selected objects of the present invention,there is provided new or improved batteries, separators, components,and/or compositions having heavy metal removal capabilities and/ormethods of manufacture and/or methods of use thereof; new or improvedlead acid batteries, lead acid battery separators (single ormulti-layer), lead acid battery components (such as battery casings,battery parts, porous bags, laminates, coatings, surfaces, fillers,electrodes, electrolytes, and/or the like) and/or polymer or resincompositions having heavy metal removal capabilities and/or methods ofmanufacture and/or methods of use thereof; new or improved lead acidbatteries, lead acid battery separators (single or multi-layer), leadacid battery components (such as battery casings, battery parts, porousbags, laminates, coatings, surfaces, fillers, electrodes, electrodeformulations, electrolytes, and/or the like) and/or polymer or resincompositions having heavy metal removal capabilities and utilizing atleast one source of natural and/or synthetic hydroxyapatite having heavymetal binding capabilities, preferably having at least one PIMS mineralas at least one filler component therein; particular microporouslead-acid battery separator embodiments wherein the PIMS mineral(preferably fish meal, a bio-mineral) is provided as at least a partialsubstitution for the silica filler component in a silica filled leadacid battery separator (preferably a polyethylene/silica separatorformulation); battery separators, to methods of manufacture of batteryseparators, to methods of use of battery separators, to improved batteryseparators, and/or to improved separators or laminates for lead acidbatteries; and/or the like.

BRIEF DESCRIPTION OF THE DRAWINGS

Drawing sheets 1 to 33 are respective slides, illustrations, text,charts, and/or images and are fully made part of this application andrelied upon for all they show and disclose. For example, FIGS. 5, 26,27, and 32 illustrate possibly preferred separator embodiments.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with at least selected embodiments, examples, or objectsof the present invention, there are provided new or improved batteryseparators, batteries, systems, components, compositions, and/or methodsof manufacture and/or methods of use; new, improved, unique, and/orcomplex performance battery separators, lead acid battery separators,flooded lead acid battery separators, enhanced flooded lead acid batteryseparators, ISS or micro-hybrid battery separators, ISS flooded leadacid battery separators, ISS enhanced flooded lead acid batteryseparators, batteries including such separators, systems or vehiclesincluding such batteries or separators, and/or methods of production,and/or methods of use; and/or the like.

In accordance with at least selected embodiments, examples, aspects, orobjects of the present invention, the preferred separator, batteryand/or electrical system preferably includes one or more, morepreferably includes two or more, and possibly most preferably includesthree or more of the following possibly preferred improvements,features, changes, modifications, enhancements, performance,characteristics, profiles, shapes, configurations, structures, parts,attributes, spacing, thicknesses, ratios, blends, mixtures,formulations, additives, agents, coatings, layers, laminates, mats,non-wovens, surfaces, inclusions, effects, embodiments, examples,combinations, sub combinations, and/or the like:

1) Charge Acceptance/Power Delivery—preferred features or changes to theseparator to help increase charge acceptance/power delivery:

-   -   a. Low or Lower Electrical Resistance (ER)—In order to maximize        charge acceptance during regenerative braking and power delivery        during restart of the internal combustion engine, it may be        important to minimize the separator ER. The separator ER can be        lowered via the following methods:        -   i. Lower Back-Web (BW) Thickness—As the BW thickness is the            main contributor to separator ER, this can be reduced from            typical values which range from 150 to 250 micron. However            as this is done, the material may become very challenging to            process on typical envelopers. Here it is recommended to            lower the BW thickness between 75 to 150 microns and then            reinforce the transversal stiffness with the use of negative            cross ribs. (See FIGS. 5 and 6)        -   ii. Increase Silica to Polymer Ratio—A second method to            reduce ER in the separator is to increase the loading of            silica, relative to the polymer content. One possibly            significant issue with this change is that the oxidation            resistance of the separator may be compromised to some            degree. In a standard SLI battery, the battery is subjected            to heavy overcharging, wherein oxidizing species are            generated in the positive plate. However, in ISS            applications, the battery will not be generating oxidizing            species as overcharge situations will be limited by design            of the electrical system, therefore the separator will not            be required to have as much oxidation resistance as is            required in a typical SLI application. The silica to polymer            ratio could vary from about 3.0/1.0 to 5.0/1.0.        -   iii. Utilize High Oil Absorption (High Surface Area) Silica            (Increase Porosity)—A third approach to reduce the separator            ER is to utilize a silica with a high surface area            (e.g. >200 g/m2), which typically yields a high oil            absorption. With this type of silica, the amount of pore            forming agent can be increased from 60 to 65% by weight to            70 to 80% in the extrusion process and thus yields a            significantly higher final porosity and lower electrical            resistance. (See FIG. 11)    -   b. Minimize Gas Entrapment—It has been recognized that hydrogen        and oxygen gas generated by the battery active materials during        charge and discharge may become trapped by the separator,        insulating a portion of the plate and rendering it unable to        partake in charge and discharge reactions. This may ultimately        limit the ability of the battery to accept charge and deliver        power. Following are some specific changes to reduce the        opportunity for gas entrapment:        -   i. Laminate Structure and Modifications—In a number of the            designs that have been proposed for ISS batteries, a            laminate structure has been incorporated into the separator            in order to help retain the positive active material (PAM)            in the positive plate. In general, these laminates tend to            increase the amount of gas entrapped in the cell. (See FIGS.            12 and 13) By modifying the laminate structure, it is            anticipated that gas entrapment could be reduced            significantly. Potential preferred modifications could be:            -   1. Treatment of the laminate with a chemical or plasma                to modify surface energy to shed gas bubbles.            -   2. Perforation to allow bubbles an area to coagulate and                escape the laminate matrix.            -   3. Addition of nucleating agents.            -   4. Changing the structure of the laminate during                formation.            -   5. Addition of polymer fibers and/or shaped polymer                fibers to the laminate structure.            -   6. Addition of wetting agents (surfactants).            -   7. Change the orientation on the fiber structure of the                laminate so gas bubbles are less likely to attach to the                structure.            -   8. Minimize the thickness of the structure so that there                are simply less sites for bubble adhesion.        -   ii. Wetting Agent Selection—It has been demonstrated that            the selection of a wetting agent for use on the polyethylene            separator can have a significant influence on the retention            of gas bubbles in the cell. It is understood that wetting            agents with more hydrophobic behavior may exhibit better            performance in this aspect than those that tend to be            hydrophilic. For example, ethoxylated fatty alcohols are            generally preferred over substituted sulfosuccinates.        -   iii. Separator Cross-Ribs (Negative and/or Positive)—In            testing performed to examine gassing behavior, it has been            noted that small negative cross ribs appear to assist in the            nucleation and/or transport of gas bubbles to the outside of            the cell, allowing the gas to escape from between the            plates, reducing the potential for gas entrapment.        -   iv. Nucleation of Gas—A wide variety of modifications may be            made to the separator in order to assist in providing areas            on the separator to act as nucleation sites for gas bubbles            to quickly and efficiently grow to the point where they are            released from the separator and travel out of the area            between the plates.            -   1. Profile Shape (Roughness)—By incorporating certain                nanostructures onto the surface of the polyethylene                separator, gas nucleation may be increased                significantly. These nanostructures may take the form of                pyramids, chevrons, or pillars, as examples. They may be                formed by calendaring, laser ablation or controlled                chemical oxidation.            -   2. Additives—Additives may be incorporated into the                matrix of the separator (or on the surface) in order to                provide areas on the surface where they change the                surface structure or energy. These changes will                encourage the nucleation of small gas bubbles generated                to a critical volume. Examples of these additives are                carbon fibers, carbon nanotubes, or barium sulfate.

2) Hydration Shorts (Hinder, Delay, Reduce, Eliminate)—This type ofshort circuit is formed in batteries when they are allowed to stay atvery low acid concentrations for an extended period of time. Thisphenomenon is well known in the battery industry, as is adding sodiumsulfate to the electrolyte to hinder hydration shorts. In an ISSapplication, where the battery seldom receives a full charge, the dangerof forming hydration shorts is believed to be significantly greater thanin a typical SLI battery. The following are some of the significantnovel separator changes that may help reduce the occurrence of hydrationshorts:

-   -   a. Common Ion Effect—It is well known that the addition of        sodium sulfate to the battery electrolyte will inhibit the        formation of hydration shorts, via the Common Ion Effect. In the        present variants, sodium sulfate is incorporated into the        separator matrix and/or the laminate materials (such as by        impregnation), allowing the sodium sulfate to be in the proper        location to most efficiently reduce the chance of formation of        hydration shorts.    -   b. Heavy Metal Sequestration—By irreversibly adsorbing and        sequestering lead ions that are in solution, certain additives        could be incorporated into the separator (or on the separator        surface, in the laminate material, in the electrolyte, in the        battery casing, and/or the like) to inhibit hydration short        formation. Examples of materials that may be used for this        include apatite, hydroxyapatite minerals, ground fish meal,        zeolites, lignins, latex, and rubber-derivatives.    -   c. Location of Additives—It should be noted that the additives        associated with the Common Ion Effect or the Sequestration of        Heavy Metals can be added directly to the matrix of the        separator (preferably as a substitution filler for part of the        silica), coated on the separator, coated on or contained in the        laminate structure, coated onto the container of the battery        case either before or after the injection molding process,        placed in porous bags or sachets in the electrolyte or laminate        structure, and/or the like.    -   d. Lower or Reduced Acid Displacement—If the separator were        capable of displacing less acid, then the total amount of        sulfate ions in the acid solution would be higher, resulting in        a retardation of the hydration effect. In other words, this        would be an additional buffer against the over-discharge of the        battery. In order to accomplish this, potential preferred        separator modifications may include:        -   i. Thin Backweb—Lower backweb (BW) thickness with added            cross ribs (preferably negative cross ribs as discussed            above), higher porosity, and/or less rib mass of the            separator.        -   ii. Serrated/Battlement Ribs—A serrated or battlement rib            design may be used to remove mass from the ribs. This            concept is detailed in U.S. Pat. No. 7,094,498 hereby            incorporated by reference. By modifying the rib design in            this way, the separator will have less acid displacement.

3) Improve Cycle Life—In order to meet the expectations of both thebattery and vehicle manufacturers, the cycle life of a typical lead acidbattery should be improved, particularly when the battery is subjectedto high temperatures and a heavy cycling duty. One school of thought isto reduce the state of charge of the battery to reduce the amount ofovercharge and subsequent corrosion of the positive plate. However, byfollowing this route, the chance of having hydration shorts increasesdramatically. By modifying the separator, these potential issues may beeliminated. A few of the potential preferred modifications are detailedbelow.

-   -   a. Laminate Structure—In many deep cycle lead-acid batteries,        laminates are utilized to retain the positive active mass in the        positive grid. This structure eventually incorporated into the        positive plate due to the natural expansion of the positive        active mass during cycling operation. This allows the positive        active mass to maintain intimate contact, and therefore capacity        for a significantly longer period of time than otherwise        possible. It is anticipated that separators for flooded ISS        applications will incorporate a laminate, as the anticipated        duty cycle and environment will be harsh.        -   i. Glass Mat—In many flooded lead-acid batteries, glass mats            are utilized in order to help retain intimate contact            between the positive active material and the positive grid.            One potential present preferred variant envisioned for ISS            will continue to utilize glass mats, albeit with the            potential to mix different fiber lengths and widths in the            mats ranging in compressed thickness from 0.1 mm to 1.0 mm.            Preferably a new or improved separator for flooded ISS            applications will incorporate this laminate.        -   ii. Synthetic Nonwovens—Nonwoven polymeric mats have also            been utilized recently as active material retainers in            lead-acid batteries. These materials are typically made of            polyester. (refer to Polymat published patent application,            US 2006/0141350 A1, hereby incorporated by reference herein)            Preferably a new or improved separator for flooded ISS            applications will incorporate this laminate.        -   iii. Hybrid—It is imagined that hybrids of glass mixed with            polymers may be incorporated into a hybrid mat, which will            have the rigidity and oxidation resistance inherent in the            glass with the tear resistance and toughness of nonwovens.            By combining the properties of both materials, a mat with            superior properties for the battery may be produced.            Preferably a new or improved separator for flooded ISS            applications will incorporate this laminate.    -   b. Profile Selection—The selection of a profile or ribbing        design is not often considered for adding benefits to a typical        flooded lead-acid battery. For ISS applications, however, it is        believed that the profile design may have a much greater impact        on the battery performance. The goal of having lower acid        displacement may be contributed to by the profile design.        Conversely, it is established within the industry that tighter        rib spacing is beneficial for deep cycle applications. A unique        compromise between the two may be required. For example, a new        or improved profile having tight rib spacing with shorter rib        height, narrower ribs, battlement ribs, or the like.    -   c. Polyaspartic Acid—Polyaspartic acid retards crystal        formation. In accordance with the present invention,        polyaspartic acid can be added directly to the matrix of the        separator (this monolithic approach is preferred), coated on the        separator, coated on or contained in the laminate structure,        coated onto the container of the battery case either before or        after the injection molding process, placed in porous bags or        sachets in the electrolyte or laminate structure, and/or the        like.    -   d. Compression—A compressible, flexible and/or resilient rib        structure may enhance cycle life. For example, an I-beam rib        profile may provide the desired compression.

4) Acid Stratification—In a variety of flooded lead-acid batteries, thestratification of acid in the electrolyte has been an issue inapplications with heavy cycling requirements and few complete recharges.When a battery cycles repeatedly, but is not fully charged, orovercharged, the acid in the battery can separate, to the point wherethere will be water at the top of the battery, and concentrated sulfuricacid at the bottom. Typically, battery manufacturers will specify that abattery should be overcharged to some degree, promoting the electrolysisof water. The hydrogen and oxygen produced during this overcharging willagitate the electrolyte, mixing the water and acid. As mentionedearlier, in ISS applications, batteries will be maintained in PSoCconditions with few opportunities for overcharging to mix the acid.Therefore, any potential benefits to either acid mixing or retardationof acid stratification from the separator may be critical.

-   -   a. Profile Selection—As mentioned earlier, profile selection may        be a critical attribute for a number of properties. Another        benefit may come from the incorporation of horizontal ribs        across the surface of the separator in acting as a physical        barrier to acid stratification. It is imagined that these        cross-ribs could take a wide range of forms (reference the above        mentioned negative cross-rib patent application and positive        cross-rib patent).    -   b. Laminate Structure—The laminate structure attached to the        polyethylene separator may also serve to discourage acid        stratification. By aligning the fibers in a certain pattern        across and through the material, it is envisioned that the glass        mat may help to keep the acid from become stratified. Also,        adding the laminate structure to both the positive and negative        face of the polyethylene separator may also serve to reduce acid        stratification.    -   c. Surface Area—Minimizing the acid stratification may also be        accomplished by increasing the surface area of the separator        structure. This can be accomplished by first decreasing the        fiber diameter of the laminate structure or second by increasing        the internal surface of the separator by the type or        concentration of silica, adding porosity, having cross ribs,        and/or the like.    -   d. Acid Immobilization—Minimizing the acid stratification may        also be accomplished by immobilizing the acid. This can be        accomplished by, for example, having cross ribs which tend to        hold the acid in place (see FIG. 26), adding a silica layer on        the laminate and/or separator surface or adding silica in the        laminate to “gel” the acid and immobilize it, utilizing Daramic        AJS technology, or the like.

5) VRLA—It is also recognized that valve-regulated lead acid (VRLA)batteries may have a role in the market for automotive ISS applications.In this type of construction, the electrolyte is absorbed and held inthe matrix of the separator. Predominant technologies for this are usingan absorptive glass mat (AGM) separator, or gelling the electrolyte,typically with silica as the binding agent. A few novel approaches toVRLA technology are reviewed below in some detail.

-   -   a. Acid Jellifying Separator—The acid jellifying separator (AJS)        is a concept that has been utilized in the past. By modifying        the separator to incorporate high surface area silica with a        high loading of such silica in the polyethylene separator, a new        or improved product has been produced that allows the separator        to absorb enough acid to make it a viable separator for a VRLA        design. This new Daramic AJS separator may allow a manufacturer        to utilize standard flooded battery construction equipment and        techniques to produce a VRLA product. The Daramic AJS separator        will have superior behavior in improving cycling, as it is in        intimate contact with the positive plate, preventing shedding of        the active material. It will also prevent acid stratification        issues, as the polymer matrix along with the silica will inhibit        the flow and separation of the electrolyte.    -   b. Polyethylene/Absorptive Glass Mat Hybrid—One of the key        limiting factors in reducing plate spacing in batteries with AGM        separators is the ability of AGM to hold up against plate        defects and prevent short circuits from occurring. Typically,        these short circuits do not show up until after the battery has        gone through the complete assembly and charging process, adding        to the high cost of this type of product. By incorporating a        flat PE separator membrane into or on one side of the AGM        separator, the plate spacing in the battery may be reduced        without increasing failures in early life. The PE separator will        act as a shield, reducing the possibility that minor plate        defects will cause a short circuit.    -   c. Other Laminate Hybrids—It is imagined that other laminate        systems, whether nonwovens or other glass mats could be utilized        in conjunction with a flat PE separator membrane to make an        acceptable VRLA separator.

The inventive lead-acid storage battery may be required not only tosupply power as a main power supply for electric cars, but also toprovide a new function as a power supply for starting and recoveringregenerative current for hybrid electric cars, simplified hybrid carsand ISS-compatible cars having an idle stop and start (ISS) function.

The complete description and drawings of separators with negative crossribs of various configurations and methods of U.S. patent applicationSer. No. 61/253,096, filed on Oct. 20, 2009, entitled “LEAD ACID BATTERYSEPARATORS WITH CROSS RIBS AND RELATED METHODS” and of pending U.S.patent application Ser. No. 12/904,371, filed on Oct. 14, 2010, entitled“BATTERY SEPARATORS WITH CROSS RIBS AND RELATED METHODS” are each herebyfully incorporated by reference herein.

To maintain and even improve the runability of the separator, we proposeto increase the bending stiffness of the separator with tightly spacedtransverse ribs on the side of the separator facing the negativeelectrode. (See FIGS. 5 and 26) Multiple tests on commercial enveloperswith Daramic Duralife® separators which include the negative cross ribshave shown substantial improvements in processing yields when comparingseparators with the standard flat surface. (See FIG. 25) Increasing thebending stiffness results in improved enveloper processing and now weconsider separators with thinner baseweb or backweb (BW) thickness suchthat we can foresee further decreases in separator electrical resistanceby as much as 25%.

By decreasing the separator thickness, we see a two-fold benefit to thebattery performance. First off, with 25% lower separator electricalresistance; the result will be improved power delivery and chargeacceptance of the battery. Second, with less volume occupied by theseparator, there will be more acid between the electrodes. As manybatteries are designed to be electrolyte starved, replacing separatormass with acid can only yield benefits in terms of electrical storagecapacity of the battery.

There are other considerations for lowering separator electricalresistance and increasing the amount of acid between the electrodes.Today, the typical PE separator has a porosity of 60%, or to say itanother way, 40% of the separator volume is occupied by mass. If wereduce the mass of the separator by half, say to 20%, the electricalresistance will be reduced in similar proportion and result in 80%separator porosity. To confirm our assumptions we have producedexperimental separators with varying porosity and measured the resultantelectrical resistance. (See FIG. 7)

By utilizing a special type of silica (high surface area), the PEseparator can be made with very high porosity and result in lowerelectrical resistance. The preferred separator with the ultimate lowestelectrical resistance could be constructed by marrying the negativecross rib with the thin BW thickness and very high porosity (newsilica).

There is another method that we think will lower the functionalelectrical resistance of the separator thus yield improvements inbattery performance. We purposely used the term ‘functional’ electricalresistance and this we want to compare to the ‘measured’ electricalresistance of the separator. (See FIGS. 8 and 10) Today the separatorelectrical resistance is often quantified with a device where voltage isapplied across a single paired electrode chemical cell. The resistanceis measured with and without the separator between the electrodes thusquantifying the electrical resistance of the separator. Though thismethod is of value for predicting the influence of the separator onbattery performance, we think there is an important element missing,namely gas entrapment.

During formation or a charging event, once the electrodes are charged,oxygen and hydrogen are produced at the positive and negative electrodesrespectively. As electrolyte quickly becomes saturated with these gases,bubbles are produced. As these bubbles in the electrolyte form they willcoalesce and finally rise to the surface of the electrolyte similar tothe carbon dioxide in a freshly poured glass of beer. However, theprocess of evacuating the gases is relatively slow and the impact uponbattery performance is profound. Like the glass of beer, these tinybubbles attached to various surfaces including that of the separator.Where the bubbles are attached there is a lack of electrolyte and theseregions become areas of high resistance. Therefore, the ‘functional’electrical resistance of the separator can be described as the measuredelectrical resistance and with the proportion of the surface area thatis blinded by these gas bubbles taken into account.

To measure the entrapped gas, cells were prepared with standard andmodified separators. (See FIG. 9) After formation and overcharging theelectrolyte level was recorded for each cell, a vacuum was pulled toevacuate the gases; the difference in level is what we define as theentrapped gas. To establish a base line, cells were tested withoutseparators; instead glass rods were used to maintain electrode spacing.From this work we can gain information regarding the amount of gasentrapment associated with the electrodes. As you can see from the belowTable 5, adding standard separators more than doubles the amount of gastrapped when compared to cells without separators. With the modifiedseparator, namely Daramic Duralife® with negative cross ribs, we canreduce the gas entrapment associated with the standard separator byapproximately 50%.

TABLE 5 Height Change after Est. Gas gas evacuation Volume Description(mm) (cc) Cell with no separator (glass rods) 6.9 52.3 Cell withstandard separator 15.6 118.0 Standard separator (Minus Plate) 65.7 Cellwith no separator (glass rods) 6.9 52.3 Cell with DuraLife ® separator11.6 87.8 DuraLife ® separator (Minus Plate) 35.5

Earlier, we proposed methods for lowering separator electricalresistance by adding negative cross ribs to improved enveloperrunnability, which opens the door for processing separator materialswith thinner backweb thickness than are currently available today.Initially one might be concerned that the negative cross ribs wouldactually increase gas entrapment. It is important to note here that thenegative cross rib was one of the changes included with the DaramicDuralife® separator which had less gas trapped than the standardseparator. We have theorized that the negative cross rib pattern mayserve as a medium for coalescence of the small gas bubbles into largerbubbles so that the buoyancy forces become greater than the surfaceadhesion forces and allow the gases to escape faster than when usingstandard separators.

Thus far, we have demonstrated methods to lower the electricalresistance by 25 to 50% as compared to standard separators with twoindependent actions. Through our testing we have also found methods toreduce the amount of gas entrapped on the separator surface by more than40% which should yield an equivalent reduction in functional separatorelectrical resistance. By combining all these changes together, onecould expect to see the functional resistance decrease to 50 to 25% ofthe typical separator value. This can provide improvement for powerdelivery and charge acceptance in Micro Hybrid batteries, ISS batteries,etc.

We proposed that the Micro Hybrid battery was a cross between a highpower automobile battery and a high energy deep cycling battery. So letus spend a few minutes considering improvements to the deep cyclingaspect required in the application. When a lead acid battery is cycledfrequently or deeply the positive active material will shed, thenegative active material will sulfate, the negative lugs may thin, theacid is likely to stratify especially when operated in a partial stateof charge and finally hydration shorts may develop through theseparator. Many design options are being explored to address thesesituations but let's review those associated with the separators. If wecan keep the active material in place longer, then we can extend thefunctional life of the battery. To prevent shedding of the activematerial, there are two options: First the number of ribs on theseparator can be increased thus providing more points of contact forkeeping the positive active material in place; and, Second is to add alaminate, such as glass-mat to the separator.

The laminate provides a positive support to prevent the shedding ofpositive active material. However these laminates must be carefullyselected so as not to increase gas entrapment, which will increase thefunctional electrical resistance, and lower power delivery and chargeacceptance of the battery. Utilizing the method previously described, weconducted gas entrapment tests on separators with various laminates.From the laboratory work, we first determined the amount of entrappedgas associated with the plates and the separator so that we can see theinfluence of various laminates. From the testing we can see vastdifference between various laminates with regard to level of gasentrapment. Therefore to maintain good charge acceptance and powerdelivery, while maintaining good protection against shedding of positiveactive material we believe it is necessary to select the correctlaminate. (See FIGS. 12 and 13)

There is another point of synergy between cycling and good electricalperformance. In our earlier work we identified methods to increase theelectrolyte between the electrodes. This was achieved by lowering theseparator backweb thickness, increasing the separator porosity anddecreasing the amount of entrapped gas on the separator. In general, webelieve that these steps will also prevent hydration shorts, the onsetof acid stratification and the sulfation of the negative electrode. Thuswe believe that more acid between the plates will improve chargeacceptance, power delivery and extend the functional life of the batteryused in a micro-hybrid application.

To that end, we have put forth separator concepts that will yieldbattery improvements. To improve power output and charge acceptance ofthe battery, methods to lower the separator electrical resistance whichincludes 1) Implementation of negative cross rib, with the Duralife®Separator, allowing for the enveloping of thin separators and 2) Methodsto substantially increase the porosity of the separator and drasticallydecrease the electrical resistance. The aforementioned modificationswill also serve to increase the available acid between the plates andthus increase the electrical capacity of the battery when electrolytelimited. To also increase the amount of acid between the plates, weproposed methods for encouraging the gas coalescing and evacuation whichwill lead to better electrical performance.

To extend the functional performance of the lead acid battery especiallyin deep cycling applications, we proposed increasing the number of ribsto provide more contact points for the positive active material which ismore likely to shed during heavy cycling. Another method to prevent theshedding of the active material is to add a laminate to the separator.However this laminate should be carefully selected to minimize theamount of gas entrapped and thus yield the maximum power delivery andcharge acceptance of the battery. There is more to be said on extendingcycle life by minimizing the onset of acid stratification or preventinghydration shorts through the separator. (See FIG. 14).

We believe these new concepts developed for the micro hybrid applicationcan be applied immediately to existing products serving current marketneeds. For instance, improved enveloper runnability will be wellreceived benefit to the battery manufacturer looking to further improveplant efficiencies. Separator modifications that reduce the amount ofgas entrapment and thus yield improved power and electric functionalitycan be benefit to a battery manufacturer struggling to make ratings ofan existing battery.

The present invention may be well suited for microporous material (e.g.pores less than 1 micron), but it also applies to other porous andmacroporous (e.g. pores greater than 1 micron) materials includingseparators made from rubber, PVC, synthetic wood pulp (SWP), glassfibers, cellulosic fibers, polypropylene, and combinations thereof.

In accordance with at least selected embodiments or aspects, the presentinvention is directed to improved, unique, and/or high performance ISSlead acid battery separators, such as improved ISS flooded lead acidbattery separators, ISS batteries including such separators, methods ofproduction, and/or methods of use. The preferred ISS battery separatorof the present invention addresses multiple separator propertiessimultaneously and may include negative cross ribs and PIMS minerals.

The present invention is not limited to separators for ISS flooded leadacid batteries, such as polyolefin separators, preferably filledpolyethylene separators, but also applies to separators for capacitors,accumulators, gel batteries, polymer batteries, carbon batteries,battery/capacitor combinations, electrochemical cells, porous membranes,porous films, porous laminates, coated membranes, and combinationsthereof.

In accordance with at least selected embodiments or aspects, the presentinvention is directed to improved, unique, and/or complex performancebattery separators, lead acid battery separators, flooded lead acidbattery separators, enhanced flooded lead acid battery separators, ISSor micro-hybrid battery separators, ISS flooded lead acid batteryseparators, ISS enhanced flooded lead acid battery separators, batteriesincluding such separators, systems or vehicles including such batteriesor separators, methods of production, and/or methods of use.

Where current separator technology has addressed one or two keyproperties in discrete separators, one possibly preferred batteryseparator of the present invention addresses and optimizes multipleseparator properties simultaneously. It is believed that in accordancewith at least certain embodiments, the present invention is the first torecognize the need to address multiple separator propertiessimultaneously, the first to choose particular multiple separatorproperty combinations, and the first to produce commercially viablemultiple property battery separators as described below.

In order to reduce fuel consumption and generation of tail pipeemissions, auto manufacturers have implemented varying degrees ofelectrical hybridization. One form Hybrid Electric Vehicle (HEV) isoften referred as the ‘Micro HEV’ or ‘micro-hybrid’. In such Micro HEVor concepts, the automobile has the idle stop/start (ISS) function andoften regenerative braking. In order to keep costs down, many automanufacturers are considering a flooded or enhanced flooded lead acidbattery (EFB) to meet the electrical functionality associated with theISS function. As the functionality associated with this battery is oftendifferent than a standard automotive application, such as StartingLighting and Ignition (SLI) battery, this may result in differentfunctions or preferred performance of the ISS or micro-hybrid batteryseparator.

In accordance with at least selected embodiments or aspects, the presentinvention is directed to improved, unique, and/or complex performancebattery separators, lead acid battery separators, flooded lead acidbattery separators, enhanced flooded lead acid battery separators, ISSor micro-hybrid battery separators, ISS flooded lead acid batteryseparators, ISS enhanced flooded lead acid battery separators, batteriesincluding such separators, systems or vehicles including such batteriesor separators, methods of production, and/or methods of use.

Although one possibly preferred embodiment may be a vented or floodedlead acid battery, it is understood that the battery may be an enhancedflooded lead acid battery (EFB), valve-regulated lead-acid (VRLA)battery, low-maintenance lead-acid rechargeable battery, absorbed glassmat (AGM) battery, VRLA AGM battery, gel battery (gel cell), VRLA gelbattery, sealed lead-acid battery, “acid-starved” design battery,“recombinant” battery (the oxygen evolved at the positive plate willlargely recombine with the hydrogen ready to evolve on the negativeplate to create water), polymer, carbon lead acid, or other battery, acapacitor, a super capacitor, an accumulator, a battery/capacitorcombination, and/or the like.

Also, the improved separator of the present invention may find specialapplicability in ISS batteries, ISS systems, ISS vehicles, or may beused in other batteries or devices.

The advent of Micro HEV and ISS with or without regenerative breakingsets new demands on the battery and the battery separator. Such newdemands may be addressed or met by at least certain embodiments of theseparators, batteries, systems, or methods of the present invention.

The ISS flooded lead acid battery will be operated in a partial state ofcharge (PSoC), approximately 50 to 80% unlike the typical SLI batterywhich is usually operated at 100% state of charge. With regenerativebraking and frequent restarting, the battery will experience shallowcharge and recharge cycles. Depending on the design of the electricalsystem, the ISS battery may not normally go into overcharge and thusgenerate oxygen and hydrogen gas which can be useful for acid mixing.

Lead acid batteries continue to grow and expand into new applications.One growing category of application is referred to as deep cycling,where the battery is frequently and deeply discharged. Examples of suchapplications include micro-hybrid vehicles for instance, thoseassociated with idle-start-stop, power back-up, renewable energyassociated with wind or solar and traction, such as used to powerelectric fork trucks, golf carts or the like.

As lead acid batteries are being used in these deep cyclingapplications, there is much work underway, especially associated withuse in micro-hybrid vehicles to improve fitness for use. To that end,scientist are exploring various options to improve the conductivity andutilization of the active mass, prevent the deleterious effects ofsulfation, minimize grid and lug corrosion, and prevent active materialshedding, just to mention a few. (See FIG. 16) Even though the lead acidbattery has been commercially utilized for over 100 years, advances arestill being made.

In accordance with at least certain embodiments or aspects of thepresent invention, new, improved, high performance, and/or complexperformance separators can bring positive impact on extending thefunctionality of the lead acid battery in these deep cycle applications.As with the larger battery industry, much of the research work hasrecently focused on developing separators for micro-hybrid vehicles, butwe believe many of these advances will also be beneficial to the broaderdeep cycling market. To provide context, we start with the historicgains made in separator designs and finish with recent work or work thatis currently underway.

Historically, and with reference to FIG. 17, lead acid batteries usedseparator constructed of wood shingles, rubber, sintered PVC, andimpregnated cellulosic materials. As separators, these materials are indecline throughout the world for a variety of reasons. With reference toFIGS. 18 and 19, we focus on a few properties found in newer separatorsthat ultimately replaced the older technologies: 1) Pore Sizedistribution, 2) Acid Displacement, 3) Oxidative Resistance and 4)Weld-ability. To understand the importance of pore size of theseparator, we first should note that the lead particle used in theactive material has an average diameter of 1 to 5 microns. In order toinhibit migration of the lead particle through the separator and thushindering the formation of points of electronic conductance betweenelectrodes there has been a shift away from the historic separatormaterials to those with sub-micron pores such as the PE separator. (SeeFIG. 18).

The next point raised is acid displacement and by this we mean to implythe volume that is occupied by the separator. The more volume theseparator occupies, the less acid available between the electrodes. Lessseparator volume and more acid usually increases battery capacity andoften may increase discharge rating, especially when limited by acidvolume in the battery. Newer separator materials occupy less volume thantheir predecessors, and therefore they need to be more oxidativeresistant in order to function through the intended life. Simply put,separators that allow for more acid between the plates are typicallythinner in backweb thickness and thus need to better withstand oxidativeattack.

The last point of historic interest is the ability to be formed into apocket or sleeve. Often the functional life of a lead acid battery maybe cut short due to mossing, side or bottom shorts. By mossing, we meanthat active material has shed and formed a conductive bridge around theseparator side or bottom, even when there is a mud room present.Separators that can be made into a pocket or a sleeve can greatly reduceor prevent these types of failures.

Thus far, we have been speaking of the functionality of the separator inits most basic terms to separate the positive and negative electrodeswhile allowing the free flow of ions and electrolyte. With reference toFIG. 20, we look at a more active function of the separator and that issuppressing what is often called antimony poisoning. During the life ofthe battery, a portion of the antimony that is added to the positivegrid will become soluble in the electrolyte and then migrate and depositon the surface of the negative electrode. The plating out of antimonywill depolarize the negative electrode and thus put more voltage load onthe positive electrode during charging. As the battery is charged, theantimony plated on the negative electrode will initiate the hydrolysisof water before the lead sulfate is converted back to spongy lead. Thussome portion of the charging current is not stored but wasted inproducing hydrogen and oxygen from water.

To deal with this antimony issue, battery manufacturers have decreasedthe concentration of antimony or eliminated it completely. However indeep cycling applications, there are many positive benefits that resultfrom an alloying with antimony. (See FIG. 21). As the battery is deeplydischarged, the lead is converted to lead sulfate which is approximately40% more voluminous and as such will lead to expansion in the cell.Antimony alloys increase the strength of the grid and prevent harmfuldeformations and which can ultimately assist to convert the lead sulfateback to lead during charging. Next, it has been found through experiencethat antimony alloys improve the interface between active material andgrid. With improved interface, one can expect more efficient use ofactive material and improved charge acceptance. The most notable reasonfor antimony is to lower or retard the corrosion rate of the positivegrid. Without opening an advanced discussion in the science ofmetallurgy, antimony alloy is one typical design change to lower gridcorrosion especially in batteries that are frequently discharged.

In accordance with at least selected embodiments or aspects of thepresent invention, battery manufacturers can take advantage of theaforementioned benefits associated with antimony and by selecting theappropriate separator any detrimental impacts can be dealt with. Theappropriate or preferred separators are modified, new, improved, and/orcomplex performance PE separators. PE separators have been used for manyyears in deep cycling applications such as motive power, inverterbatteries, golf cart, and renewable energy and even in SLI applicationswith stringent OEM specifications for low water loss. Thus when usingantimony alloys, it is important to select the appropriate separator tofully utilize the benefits and mitigate any associate deleteriouseffects.

As stated earlier, many of the scientists associated with the lead acidbattery industry have been acutely focused recently to meet the demandsassociated with the ISS or micro-hybrid vehicles. With reference to FIG.22, the demands of the ISS or micro-hybrid application are a crossbetween the high power requirements associated with the SLI battery andthe deep cycling demands of the motive power applications.

We start with looking at modifications to the separator that can yieldmore power in the battery. More power can be harvested from the batteryas the internal resistance is reduced. By providing more acid betweenthe electrodes limitation associated with diffusion can be solved andalso yield more power. Separator resistance is often characterizedoutside of the battery in a laboratory device. Though the value derivedfrom such a device is generally useful, we think there is an importantelement missing, namely, gas entrapment. (See FIG. 23) In a flooded leadacid battery gas is generated to varying degrees depending on thecharging current. This gas will ultimately escape the battery, but for atime it will adhere to the electrode and separator surfaces. Where thegas is adhered, this is effectively a dead zone for ionic conductance.We have found methods to effectively reduce the amount of gas attachedto the separator by approximately 40%. By reducing the gas associatedwith the separator by preferably 40% or more, a significant improvementin the functional ionic resistance associated with the separator mayimprove the power performance of the battery.

Another method to improve the power of the battery is to increase theamount of acid between the electrodes. (See FIG. 24) In accordance withat least one embodiment or aspect of the present invention, this ispreferably done via stepwise modifications to the separator. First, theoxidation resistance of the separator needs to be improved so that massof the separator can be reduced without compromising the primaryfunctionality, which is to prevent electronic shorting of theelectrodes. With reduced mass, the separator still must have appropriatemechanical properties that allow it to be assembled into a battery. Twosuch properties are the resistance to puncture and bending stiffness.Once care is taken to improve the oxidation resistance while maintainingappropriate levels of puncture resistance and stiffness, the separatormass can be reduced to increase the volume of electrolyte between theelectrodes. With more acid available between the electrodes, the batteryis less likely to encounter limitations associated with acid diffusionand thus improve the power output. The table in FIG. 24 shows acomparison between selected standard Daramic® HP and DuraLife®separators, being offered now by Daramic, LLC of Charlotte, N.C. formicro-hybrid battery applications.

In comparing the two separators, we can see that the DuraLife® separatordemonstrates a substantial increase in oxidation resistance, whilemaintaining high puncture resistance that is found in Daramic® HP andthis was accomplished with approximately 15% less mass. Less mass of theseparator, also means less acid displaced by the DuraLife® separator andthus more acid between the plates. Manufacturers focusing onmicro-hybrid applications are finding batteries built with Daramic®DuraLife® separators have lower battery resistance and higher poweroutput during rapid discharge when compared to standard PE separators.

Another major challenge associated with the micro-hybrid application isthe ability to extend the cycle life of the battery. Batteries in thisapplication are often operated under a partial state of charge,discharged to varying degrees depending on the duration of time thevehicle is at a stop and the amount of electrical duty during such astop without being fully recharged between discharges.

Besides delivering a quick boost of power to restart the engine aftervarious stops, the battery may also experience tens of thousands ofshallow cycles over the expected life of the battery. As these batteriesare cycled there is an opportunity for an acid gradient to develop. (SeeFIG. 25) With the acid concentrating in the bottom of the cell, theelectro-chemical reactions will be more limited to the upper portion ofthe electrode and this will lead to premature capacity loss. In deepcycle applications, sufficient overcharge will create gas bubbles thatwill assist in mixing the acid and preventing acid stratification.However in applications where the battery is seldom if ever fullycharged, such as ISS, other means should be applied to prevent acidstratification.

To employ other means to prevent acid stratification, it is important tofirst understand the mechanism for why it is created. As electricalcurrent is applied to a battery in a partial state of charge, leadsulfate is converted and a high concentration of sulfuric acid initiallyforms at the plate surface. At this instant, a boundary layer ofsulfuric acid will set-up adjacent to the plate surface. As this acidlayer is more concentrated than the bulk acid, there will be a drivingforce to diffuse or mix with the lower concentrated acid in the bulkspace. Beside the forces of diffusion, the forces of gravity will alsobe active on this boundary layer. Unfortunately, highly concentratedsulfuric acid may be 10 to 20% heavier than the bulk acid and thisboundary layer will act like a denser column and result in the acidconcentrating the bottom of the cell. This tendency toward acidstratification is especially seen in flooded batteries operated in apartial state of charge where the acid is not immobilized by theseparator. Upon charging in a VRLA battery, the concentrated acidproduced at the electrode surface immediately comes into contact withthe glass fibers that fill the entire space between the electrodes andthe capillary action of the intersecting fibers provides a counter forceto gravity diminishing the tendency for the acid to stratify.

With the introduction of the DuraLife® separator, there are designchanges that we believe help minimize acid stratification in a floodedlead acid battery and in fact battery tests are confirming the positiveresults. First and foremost, the DuraLife® separator occupiesapproximately 15% less volume than traditional separators. Thus, betweenthe electrodes more acid will be available which is important tomaximize electrical performance. The next design parameter to note isthe preferred negative cross rib configuration. (See FIG. 26) Typically,the surface of the separator that is facing the negative electrode iseither flat or has mini-ribs in the vertical (or longitudinal)direction. (See FIG. 25)

With reference again to FIG. 26, the preferred negative cross rib designassociated with the DuraLife® separator has a multitude of smallmini-ribs in the horizontal (or transverse) direction. It is believedthat the electrolyte is immobilized to a degree as there are a multitudeof small mini-ribs in the horizontal direction. (See FIG. 26) Thesenegative cross ribs provide a mechanical barrier different butsynonymous in function with the AGM separator that will hinder the acidgradient from developing. If you like, the negative cross rib designcreates upwards of hundreds of mini-transverse dams to keep the heavieracid from flowing downward.

Besides preventing acid stratification, the design of the negative crossrib may also assist in another area. In a rapid discharge, the rate ofdiffusion of acid into the negative electrode is often a limiting factorwhen high power is required. Therefore, the negative cross rib designcreates hundreds mini dams, which in turns creates hundreds mini poolsof acid uniformly across the surface of the electrode. Thus far, we haveaddressed the possible mechanisms for preventing acid stratification andimproving power delivery. The DuraLife® separator has been found toimprove power delivery and reduced acid stratification in Micro-hybridbattery testing. With further testing, we will even better understandthe various mechanisms and thus further enhance the contributions thatthe separator can add in these new applications.

Another aspect to extending the life of a deep cycling battery is toinhibit the shedding of the positive active material. To that end,separators are often combined with a non-woven laminate such as a glassmat. (See FIG. 27) The laminate structure is typically applied to thesurface of the separator which is in direct contact with the positiveelectrode. For years this has been a typical commercial approach forextending the functional life of deep cycling batteries. However, theold laminate structure lowered the power output of the battery. Inmicro-hybrid batteries, the application requires that we simultaneouslyimprove both the cycling ability and the power output.

Thus, work has recently been undertaken to optimize laminate structuresfor micro-hybrid applications. First, the laminate should maintain themechanical properties to prevent shedding of the active material overthe intended life of the battery. To meet this requirement, the laminateshould be constructed with a fiber structure and of materials that areresistant to oxidative attack. Second, the laminate should displace aslittle acid as possible and thus ensure maximum availability of acid.Displacing as little acid as possible implies that the material is ofthe lowest basis weight. As the basis weight decreases, the mechanicalproperties usually also decline. Thus the challenge was and is tooptimize the properties simultaneously. There is another challengecreated by low basis weight laminates which is the point of bonding ofthe two materials (separator, laminate). A normal technique forcombining the materials is to apply adhesive to the rib surface of theseparator and the laminate, but with thinner laminates, the adhesivewill often wick to the next layer and create processing problems.Another bonding approach is to sonically weld the laminate structure tothe rib top and thus eliminate the adhesive from the system alltogether. This kind of approach may only be practical when the laminatehas a sufficient amount of synthetic fibers in the mat.

There is another laminate criterion that is not inherently obvious butcan substantially limit the energy conversion of the battery, namely gasentrapment. Anytime a lead acid battery is overcharged, hydrogen andoxygen are formed due to the hydrolysis of water. In a flooded battery,these gases will ultimately escape. However, for a time, these gaseswill adhere to the surfaces of the electrodes, separator and especiallyto the laminate structure incorporated to extend the cycle life of thebattery. As the gas is entrapped, the electrolyte is pushed out of thespace between the electrodes as demonstrated by the raise in the heightof the electrolyte in the battery. As gases are a terrific insulator,the paths of ionic conductance are greatly reduced. Thus optimization ofthe laminate to minimize gas entrapment is possibly critical formaximizing power and electrical capacity of the lead acid battery eitherin deep cycle or micro-hybrid applications.

With reference to FIG. 28, a recap is in order. Over the past 100 yearslead acid batteries have advanced mostly in an evolutionary manner tothe various demands of new applications. To meet these demands, changeshave occurred in materials of construction, including the separators.Over this time, separators have migrated toward synthetic materials ofconstruction such as Ultra High Molecular Weight Polyethylene (UHMWPE).These synthetic materials have allowed the separator to be micro-porousfor short prevention, improved the oxidation resistance to extend thelife, and to be envelope-able so as to prevent side and bottom shorts.These new types of PE separators have offered the potential to add otherfunctionality such as the incorporation of additives into the separatorto prevent antimony poisoning and decrease the associated water loss.

To meet new market opportunities such as micro-hybrid, we are surechanges have been and will be required to the materials of constructionincluding the separator. (See FIG. 29) The micro-hybrid applicationrequires high power to crank the engines as is found in traditional SLIbatteries and the frequent cycling found in deep discharge batteries. Toenhance power, we have preferably changed the separator to increase theavailable acid and lower the electrical resistance by minimizing the gasentrapment of the separator. To extend battery life, we have preferablyimmobilized the acid and thus prevented the onset of acidstratification. Next, we added laminates to keep the active material inplace. These design changes preferably focus on optimizing threeproperties of the laminate simultaneously: basis weight, mechanicalproperties and gas entrapment. Not only have design changes been madeand proposed, but at least certain of the separator and laminate changeshave also been validated to improve the performance of micro-hybridflooded batteries.

Meeting the challenges associated with the micro-hybrid application mayhave benefits in other applications currently served by lead acidbatteries. For instance, modifications to the separator to minimize acidstratification, reduced gas entrapment, maximize acid amount, reduceelectrical resistance and extend cycle life can all be directlytransferrable in current battery applications. These evolutionarychanges produced a revolutionary separator, and associated with theinherent favorable cost structure verses competing technologies, makethe lead acid battery an excellent choice for the developing ISS andmicro-hybrid markets.

In accordance with at least selected embodiments, the preferred new,improved and/or complex performance separator, such as a deep cycle orISS or micro-hybrid separator, has features that help minimize acidstratification in a flooded lead acid battery, occupies approximately15% less volume than tradition separators, has negative cross ribs, hasa multitude of small mini-ribs in the horizontal direction, has amechanical barrier that will hinder an acid gradient from developing,has hundreds of mini dams to keep heavier acid from flowing downward,has hundreds of mini dams which create hundreds of mini pools of aciduniformly across the surface of the electrode, that improve powerdelivery and reduce acid stratification in micro-hybrid batteries,and/or the like.

In accordance with at least selected objects of the present invention,there is provided improved, unique, high performance, and/or complexperformance battery separators, lead acid battery separators, floodedlead acid battery separators, enhanced flooded lead acid batteryseparators, ISS or micro-hybrid battery separators, ISS flooded leadacid battery separators, ISS enhanced flooded lead acid batteryseparators, batteries including such separators, systems or vehiclesincluding such batteries or separators, methods of production, methodsof use, and/or the like. FIGS. 31 to 34 are directed to leaf or piecetype separators. FIG. 31 is a schematic perspective view representationof an exemplary lead acid battery, with parts broken away, illustratingan outward placement of a leaf or piece separator such as the Daramic®Auto PE Leaf Separator or the Daramic® Industrial PE Leaf Separator ofFIG. 33. The Daramic® PE Leaf Separators of FIG. 33 are shown withoptional glassmat laminate (see the respective enlarged end views).

In accordance with at least selected embodiments, the present inventionis directed to new or improved batteries, separators, components, and/orcompositions having heavy metal removal capabilities and/or methods ofmanufacture and/or methods of use thereof. In accordance with at leastcertain possibly preferred embodiments, the present invention isdirected to new or improved lead acid batteries, lead acid batteryseparators (single or multi-layer), lead acid battery components (suchas battery casings, battery parts, porous bags, laminates, coatings,surfaces, fillers, electrode formulations, electrolytes, and/or thelike) and/or polymer or resin compositions having heavy metal removalcapabilities and/or methods of manufacture and/or methods of usethereof. In accordance with at least possibly more preferred particularembodiments, the present invention is directed to new or improved leadacid batteries, lead acid battery separators (single or multi-layer),lead acid battery components (such as battery casings, battery parts,porous bags, laminates, coatings, surfaces, fillers, electrodeformulations, electrolytes, and/or the like) and/or polymer or resincompositions having heavy metal removal capabilities and utilizing atleast one PIMS mineral as at least one filler component therein. Inaccordance with at least one particular microporous lead-acid batteryseparator embodiment, the PIMS mineral (preferably fish meal, abio-mineral) is provided as at least a partial substitution for thesilica filler component in a silica filled lead acid battery separator(preferably a polyethylene/silica separator formulation). In accordancewith at least certain embodiments or examples, the invention is directedto battery separators, to methods of manufacture of battery separators,to methods of use of battery separators, to improved battery separators,and/or to improved separators or laminates for lead acid batteries.

In accordance with at least selected embodiments, the present inventionis directed to new or improved batteries, separators, components, and/orcompositions having heavy metal removal capabilities and/or methods ofmanufacture and/or methods of use thereof. In accordance with at leastcertain possibly preferred embodiments, the present invention isdirected to new or improved lead acid batteries, lead acid batteryseparators (single or multi-layer), lead acid battery components (suchas battery casings, battery parts, porous bags, laminates, coatings,surfaces, fillers, electrodes, electrode formulations, electrolytes,and/or the like) and/or polymer or resin compositions having heavy metalremoval capabilities and/or methods of manufacture and/or methods of usethereof. In accordance with at least possibly more preferred particularembodiments, the present invention is directed to new or improved leadacid batteries, lead acid battery separators (single or multi-layer),lead acid battery components (such as battery casings, battery parts,porous bags, laminates, coatings, surfaces, fillers, electrodes,electrode formulations, electrolytes, and/or the like) and/or polymer orresin compositions having heavy metal removal capabilities and utilizingat least one source of natural or synthetic hydroxyapatite having heavymetal binding capabilities, preferably at least one PIMS mineral as atleast one filler or component therein or thereon. In accordance with oneparticular microporous lead-acid battery separator embodiment orexample, the PIMS mineral (preferably fish meal, a bio-mineral) isprovided as at least a partial substitution for the silica fillercomponent in a silica filled lead acid battery separator (preferably apolyethylene/silica separator formulation).

In accordance with at least selected embodiments of the presentinvention, a believed novel concept of utilizing “Phosphate InducedMetal Stabilization” (PIMS) minerals as a filler component within amicroporous lead-acid battery separator is provided. In accordance withone particular embodiment or example, the PIMS mineral (preferably fishmeal, a bio-mineral) is provided as at least a partial substitution forthe silica filler component in contemporary silica filled lead acidbattery separator (preferably a polyethylene/silica separatorformulation).

As mentioned above, a common failure mode within the lead-acid batteryindustry is the phenomenon of “hydration shorts”. In accordance with atleast selected embodiments, the present invention is directed to new orimproved batteries, separators, components, and/or compositions havingheavy metal removal capabilities that address, delay, reduce, oreliminate the phenomenon of “hydration shorts”.

In accordance with the present invention, a variety of PIMS mineralshave been identified and some of which have been evaluated for leadaffinity (see Tables I and II below). A PIMS mineral derived from fishbone (such as commercial, lab ground fish meal) has been shown to havethe greatest affinity for lead ion over the other samples evaluated. Thefish bone or fish meal powder was extruded via pilot operation into atypical lead-acid battery separator format at several loadingconcentrations. The resulting PIMS incorporating separator was evaluatedfor lead removal efficiency; the separator demonstrated substantialreduction of lead concentration in acidic solution. For example, % Pbreductions of about 17% to 100% were demonstrated. It is preferred thatthe fish bone powder be added to substitute for the silica filler atsubstitution levels of about 1% to 20% of the silica, more preferablyabout 2% to 10%, and most preferably at about 2% to 5%. In accordancewith at least other certain embodiments, it is preferred that the groundfish bone powder (ground fish meal) be added to substitute for a portionof the silica filler at substitution levels of about 1% to 50% or moreof the silica, more preferably about 5% to 30%, and most preferably atabout 10% to 20%.

It is believed that this is the first commercial use of a bio-mineral ina battery separator, in an extruded polyolefin polymer resin, and in aporous polymer film or membrane.

In accordance with at least selected embodiments, lead reduction isachieved by incorporating PIMS minerals in lead-acid battery separators,preferably incorporating PIMS mineral derived from fish bone.

The present invention represents a novel microporous membrane substratewith chemically active properties. A range of various chemically activeor reactive mineral fillers are available and amenable to the separatorextrusion and extraction process. These minerals are available at lowcost in desired purity and in the case of fish bone (or fish meal) areindustrial by-products available from multiple sources. Advantagesinclude low cost of raw material as well as identified batterymanufacturer need to streamline existing production processes involvingsodium sulfate.

The preferred separators are microporous materials (e.g. porous lessthan 1 micron). Nonetheless, other materials such as porous ormacroporous materials are contemplated. For example, macroporousseparators (e.g. pores greater than 1 micron) would include separatorsmade from rubber, PVC, synthetic wood pulp (SWP), glass fibers,cellulosic fibers, polypropylene, and combinations thereof.

In accordance with at least selected embodiments, the battery may be alead acid or lead calcium battery such as a vented or flooded lead acidbattery, enhanced flooded lead acid battery (EFB), valve-regulatedlead-acid (VRLA) battery, low-maintenance lead-acid rechargeablebattery, absorbed glass mat (AGM) battery, VRLA AGM battery, gel battery(gel cell), VRLA gel battery, sealed lead-acid battery, recombinantbattery, polymer battery, carbon lead acid battery, or other battery,capacitor, super capacitor, accumulator, battery/capacitor combination,and/or the like. The preferred battery is a vented or flooded lead acidbattery.

In accordance with at least selected embodiments, the battery separatormay be a lead acid or lead calcium battery separator, such as a flexibleor rigid separator, a pocket, envelope, sheet, piece or leaf separator,a single or multi-layer separator, a composite or laminate separator, aseparator for a vented or flooded lead acid battery, enhanced floodedlead acid battery (EFB), valve-regulated lead-acid (VRLA) battery,low-maintenance lead-acid rechargeable battery, absorbed glass mat (AGM)battery, VRLA AGM battery, gel battery (gel cell), VRLA gel battery,sealed lead-acid battery, recombinant battery, polymer battery, carbonlead acid battery, or other battery, capacitor, super capacitor,accumulator, battery/capacitor combination, and/or the like. Thepreferred battery separator is a vented or flooded lead acid batteryseparator.

Hydroxyapatite is a mineral with demonstrated heavy metal bindingcapabilities. Hydroxyapatite can be produced synthetically and purifiedas a nano-crystalline material. Hydroxyapatite is found within theskeletal mass of many naturally occurring plants and animals (as well asa minor constituent of naturally occurring minerals such as kaolinite).The most common animal-derived sources of hydroxyapatite are aquatic(fish, crustaceans, shellfish) and land-based from bovine and porcinesources. The most common plant-derived sources of hydroxyapatite occurin tea, kelp and various species of tree bark. As with all naturalproducts, varying degrees of purity and potency may be expected. As anexample, fish meal is commercially available in a range of puritiesbased upon the level of digestion of non-skeletal remains. That is, fishmeal may contain high amounts of protein from fleshy components thatremain; this may be termed “high-nitrogen” fish meal. Fish meal that hasbeen fully processed to fully digest proteinaceous matter, leavingskeletal content intact may be termed “high-phosphorus” fish meal.

Most animal and plant derived sources of hydroxyapatite are commerciallysupplied as coarse granular materials. In accordance with at least oneembodiment, aspect or example of the present invention, in order toefficiently make use of the hydroxyapatite-bearing materials it isdesirable to perform a milling (or grinding) operation to reduce theparticle size and increase the effective surface area in an effort topromote optimal exposure of the heavy metal to the hydroxyapatite. Themilling operation also promotes ease of particle incorporation into thebattery by, for example, membrane extrusion, impregnating, coating,laminating, molding, sachet fabrication, or combinations of thesetechnologies. It is preferred, for example, to achieve a D50 particlesize of between 10 μm to 80 μm to achieve optimal condition for theincorporation of ground fish meal into a battery separator via twinscrew extrusion methodology. The aforementioned particle size range isalso desirable when incorporating natural hydroxyapatite materials intonon-woven laminate-separator structures, impregnating, coating, molding,and bulk powder sachet-type delivery methods.

In accordance with at least selected embodiments of the presentinvention, it is preferred to compound the hydroxyapatite source (i.e.ground or milled fish meal) into the separator extrusion formulation(such as a polymer/silica/fish meal formulation or a polymer/silica/fishmeal/oil formulation). Separators produced in this way offer the desiredelectrochemical performance attributes of known lead acid batteryseparators but surprisingly surpass the conventional separatorcapabilities by actively sequestering lead in solution. In deepdischarge condition, the electrolyte contains an elevated level ofreduced lead passing through the tortuous separator matrix and inaccordance with at least selected embodiments of the present inventionthe separator comprises extrusion immobilized hydroxyapatite (fish meal)to sequester elemental lead prior to migration to the negativeelectrode. Therefore, in accordance with at least selected possiblypreferred embodiments, sources of hydroxyapatite are preferablyimmobilized by incorporation into the separator extrusion process toexploit surface area contact probability and proximity to the electroderequiring protection.

Another approach to the incorporation of hydroxyapatite into theseparator and/or battery is the inclusion of the reactive mineral into alaminate mat which is adjacent to the separator and/or attached to theseparator by attachment means such as welding, spot welding, ultrasonicwelding, adhesive, heat, heat and pressure, or other known processes.The laminate may be a glass mat and the fish meal or other source ofhydroxyapatite may be mixed with a binder utilized during formation ofthe glass mat, coated on the mat, and/or impregnated in the mat. Thefish meal or other source of hydroxyapatite may be co-extruded with theresin during the fiberization process thus allowing for inclusion into“carded” dry process non-wovens as well as wet-laid processes.Alternatively, the fish meal or other source of hydroxyapatite may alsobe used within synthetic non-woven materials, such as PBT, PET, PP,and/or the like by means of addition to the binder and/or by directaddition to the furnish prior to wet-lay fiber formation. This methodalso has utility in adding fish meal or other source of hydroxyapatiteto cellulosic laminates such as “pasting papers”. One or more sources ofhydroxyapatite may also be incorporated on or in the separator by meansof, for example, coated adhesion (after separator formation), directinclusion (during formation), to both inorganic and organic fibrouslaminate materials in contact with the separator, and/or combinationsthereof.

Another approach to the incorporation of hydroxyapatite (such as groundfish meal) is to coat the fish meal directly to the positive and/ornegative surface of the separator. An example of this method is toproduce a slurry of the desired concentration, coat the positive ornegative surface with the slurry by known coating means (dip, spray,roller, nip, etc.) and subsequently dry the slurry-separator article toinsure immobilization of the fish meal during any prerequisite separatorprocessing steps prior to the battery build and formation. Therefore,sources of hydroxyapatite can be applied by mixing with a vehicle, forexample water (or other solvent or binder), to produce a slurry ormixture suitable for the application of a surface coating (preferably aporous coating).

Another approach to the incorporation of hydroxyapatite into the energystorage device is by compounding the reactive mineral, (e.g. fish meal),into the resin utilized in producing the container hardware for thebattery itself (the case, supports, dividers, cover, and/or the like).Thus, some level of contact over time may occur with electrolytesolution and the surface of the resin case, supports, dividers, topcover and associated parts comprising the battery compartment.Additionally, parts comprising the battery compartment may be injectionmolded in such a way as to incorporate active material (the reactivemineral) such as fish meal into the inner or interior surfaces thereofat relatively elevated concentrations; this is generally referred to as“in-molding”. Further, sachet devices whereby the hydroxyapatite iscontained as a bulk powder within a porous, non-woven, paper, and/orplastic enclosure or another design allowing for the storage ofhydroxyapatite in free electrolyte solution can be utilized to rapidlyor over time release the active agent (reactive mineral) into theelectrolyte (such as fish meal impregnated glass fiber, glass mat orother non-woven packing material, time release beads, a gel containingthe reactive mineral, etc.). The direct inclusion of the hydroxyapatitein the electrolyte bulk storage may be utilized to provide a fixed doseof the ingredient during electrolyte filling immediately prior tobattery formation or at any time during the battery manufacturingprocess. It is also possible to mix the hydroxyapatite (such as fishmeal) into the electrochemically active material coating which isapplied to the positive and negative electrodes respectively. Theprocess of preparing the active material chemistries and the process ofapplying the active material to the electrode grids may be modified toinclude the addition of fish meal or other hydroxyapatite material (thereactive mineral may be included in the electrochemically activeelectrode formulations). Finally, hydroxyapatite may also have utilityas an additive later in the life of the battery, for example, after asuggested service interval the battery is injected with a level ofhydroxyapatite to increase service life through continued protectionagainst depolarization of the negative electrode (and prevention of“hydration shorts”).

In accordance with selected examples and testing of hydroxyapatitematerials, the following Table I illustrates the unexpected resultsachievable with even low loading of hydroxyapatite (such as fish meal).For example, a 10% loading of fish meal as a substitution for silicafiller in the battery separator of Sample G showed an amazing 72.6%reduction in lead in the 20 ml Pb solution.

TABLE I Sample Composition weight (g) solution (ml) Pb (mg/L) % Change APb Standard Solution As received (~100 ppm from vendor) N/A 20 114Control B Hydroxyapatite mineral powder (Aldrich Reagent grade) 0.7 200.614 99.5 C Calcium Phosphate tribasic powder (Aldrich) 0.7 20 0.4399.6 D Fish Meal (Commercial, lab ground) 0.7 20 0.002 100.0 EPolyethylene separator w/Si:PE ratio of 2.6:1 (CONTROL) 1.0 20 91.3 19.9F Polyethylene separator as “E”, above w/5% fish meal substituted forsilica. 1.0 20 94.6 17.0 G Polyethylene as “E”, above but w/10% fishmeal substituted for silica. 1.0 20 31.2 72.6 Notes: All samples weresoaked without agitation in the Pb standard solution for 4 days prior toanalysis at testing service. The Pb standard solution (FisherScientific) is comprised of ~100 ppm (mg/L) Pb in a solution of Nitricacid and water. pH = 1-2 All solution samples were filtered free ofparticulate at testing service prior to testing.

The Sample E control separator (silica filled) showed a 19.9% reductionin Pb. However, the control separator data is subject to the reversibleadsorptive removal mechanism of precipitated silica. As silica contentis substituted for by the hydroxyapatite source (Sample F), theadsorptive mechanism is gradually disrupted and eventually replaced bythe PIMS sequestration binding mechanism (Sample G). In other words, thereductions in Pb in Samples F and G are permanent binding(sequestration) as compared to temporary adsorption by Sample E.

The Sample B, C and D powdered (neat) samples were readily wet-out andimmersed within the Pb assay solution; complete contact of powder tosolution was observed. The Sample E, F and G separator membrane sampleswere treated with a commercially available surfactant at levelscomparable to that utilized for typical lead-acid battery separators.

All separator membrane samples readily wet-out and immersed within thePb assay solution; complete contact to the surface and underlying poreswas observed.

In accordance with other selected examples and testing of hydroxyapatitematerials, the following Table II illustrates the surprising resultsachievable with even low loading of hydroxyapatite filler (such as fishmeal). For example, a 10% loading of fish meal as a substitution forsilica filler in the battery separator of Sample L showed an unexpected56.2% reduction in lead in the 20 ml Pb solution, while a 50% loading offish meal as a substitution for silica filler in the battery separatorof Sample M showed an amazing 99.6% reduction (substantially completeelimination) in lead in the 20 ml Pb solution.

TABLE II Pb Reduction Pb Concentration in Control Pb Concentration PostPb Post Sample Weight Standard Theoretical Exposure Exposure ID ActualID (g) (ml) (ppm) (ppm) (%) A Control Pb N/A 20 100 95.4 N/A StandardControl B Hydroxyapatite  0.11 20 100  0.7 99.3% Synthetic Mineral CCommercial  0.11 20 100  0.1 99.9% Fish Meal Powder (High PhosphorousType) D Commercial  0.11 20 100 82.1 13.9% Beef Bone Meal Powder EControl 1.6 20 100 80.7 15.4% Separator I (CSI) F  2% Beef Meal 1.6 20100 90.9  4.7% (CSI) G  5% Beef Meal 1.6 20 100 84.9 11.0% (CSI) H 10%Beef Meal 1.6 20 100 82.5 13.5% (CSI) I Control 1.6 20 100 72.6 23.9%Separator II (CSII) J  2% Fish Meal 1.6 20 100 89.1  6.6% (CSII) K  5%Fish Meal 1.6 20 100 78.9 17.3% (CSII) L 10% Fish Meal 1.6 20 100 41.856.2% (CSII) M 50% Fish Meal 1.6 20 100  0.3 99.6% (CSII) N Commercial 0.11 20 100 80.5 15.6% Loose Tea Leaves

The Samples E and I control separators (silica filled ˜70%) showedrespective 15.4% and 23.9% reductions in Pb. However, the controlseparator data is subject to the reversible adsorptive removal mechanismof precipitated silica. As silica content is substituted for by the fishmeal hydroxyapatite source (Samples J and K), the adsorptive mechanismis gradually disrupted and eventually replaced by the PIMS sequestrationbinding mechanism (Samples L and M). In other words, the reductions inPb in Samples L and M are permanent binding (sequestration) as comparedto temporary adsorption by Samples E and I.

The Samples B, C, D and N powdered (neat) samples were readily wet-outand immersed within the Pb assay solution; complete contact of powder tosolution was observed.

The Samples E to M separator membrane samples were treated with acommercially available surfactant at levels comparable to that utilizedfor typical lead-acid battery separators.

All separator membrane samples readily wet-out and immersed within thePb assay solution; complete contact to the surface and underlying poreswas observed.

The Pb assay test method was carried out via ICP/MS EPA Method 200.8

All samples were static soaked without agitation for a period of 48-72hours.

The phosphorus level of all samples Post Exposure was tested and foundto be below max acceptable levels.

A group of inorganic (mineral) compounds are known to effectively bindheavy metals such as lead, cadmium, iron, zinc and copper. The mechanismby which the minerals bind heavy metals is termed “Phosphate InducedMetal Stabilization” (PIMS) and is widely utilized for the environmentalremediation of contaminated soils and water. In environmentalapplication, bulk quantities of minerals possessing PIMS affinity fortoxic metals are mixed with contaminated soil or contained within ahousing whereby water may perfuse through the bulk mineral cake.

In accordance with certain improved environmental remediationembodiments of the present invention, we propose the novel concept ofadding at least one source of hydroxyapatite (HA) or hydroxylapatite(such as synthetic and/or natural hydroxyapatite, preferably PIMSminerals, more preferably ground fish bone or meal) to a high surfacearea polymer structure, preferably a porous polymer membrane, morepreferably a microporous polyolefin membrane (flat sheet or hollowfiber), most preferably a microporous polyethylene membrane utilizingPIMS minerals as a filler, preferably as a partial substitution for thesilica filler component of a silica filled microporous polyethylenemembrane. The hydroxyapatite mineral filled membrane can be used as afilter medium, packing, liner, or the like to facilitate removal ofheavy metals from contaminated liquids such as water.

In accordance with at least selected embodiments of the presentinvention, new or improved batteries, separators, components, and/orcompositions have heavy metal removal capabilities via chemically activeproperties provided by one or more chemically active or reactive,natural or synthetic, mineral fillers, particles, coatings, agents, andthe like, preferably bio-minerals from bone or teeth, more preferablyfish bone or meal. Such new or improved batteries, separators,components, and/or compositions have advantages of low cost of rawmaterial, lead removal, reducing the need for sodium sulfate, extendingbattery warranty, use of recycled or industrial waste or by products,and/or the like.

In accordance with at least selected embodiments of the presentinvention, we have:

-   -   Incorporated a material compatible with current separator        production processes into battery separators to systematically        bind Pb in solution and reduce the occurrence of hydration        shorts over the battery service life.    -   Incorporated a material from common (and renewable) sources:        -   Fish (Most efficient at low to very low pH)            -   Bones            -   Scales        -   Crustaceans (Functional range similar to fishmeal)            -   Exoskeleton        -   Shellfish (Most efficient in basic conditions above pH 8.5)            -   Shell        -   Beef (Functional range similar to fish meal)            -   Bones        -   Peat (Functional range near neutral pH)            -   Humus, decayed vegetative matter.        -   Tea Waste (Functional range near neutral pH)            -   By-products of tea manufacturing, stems, undesired                leaves.    -   Identified possibly preferred fish meal as from “pelagic” fish        species.        -   Small, bony fish often considered inedible by humans.        -   Shellfish may also make up a minor component.        -   Fish meal is essentially the bone and scale after            purification, wash, dry and grinding.            -   Typically between 4 and 6% residual oil remains with the                fishmeal.            -   The fishmeal is comprised of the mineral Apatite w/                formula:            -   Ca_(10-x)Na_(x)(PO₄)_(6-x)(CO₃)_(x)(OH)₂

In accordance with at least selected possibly preferred embodiments, thepresent invention is directed to battery separators having one or morePIMS minerals as a filler component, battery separators having one ormore fish bone or fish meal fillers, polyethylene and silica batteryseparators having fish bone powder substituted for at least a portion ofthe silica filler, and/or methods of manufacture or use thereof.

An exemplary lead acid battery, for example, a flooded lead acid SLIbattery, includes a negative plate (electrode) and a positive plate(electrode) with a separator sandwiched there between. These componentsare housed within a container that also includes terminal posts, vents,and gang-vent plugs. In accordance with a preferred embodiment, theseparator has transverse ribs on the surface that faces negative plateand has longitudinal ribs on the surface that faces the positive plate(see, for example, FIGS. 5 and 26). Although a particular battery isshown in FIG. 31, the inventive separator may be used in many differenttypes of batteries or devices including for example, but not limited to,sealed lead acid, flooded lead acid, ISS lead acid, combined battery andcapacitor units, other battery types, capacitors, accumulators, and/orthe like.

The possibly preferred separator of FIGS. 5 and 26, is preferably aporous polymer membrane (such as a microporous polyethylene membranehaving pores less than about 1 micron). Nevertheless, the inventiveseparators may be microporous or macroporous membranes (having poresgreater than about 1 micron) made of natural or synthetic materials,such as polyolefin, polyethylene, polypropylene, phenolic resin, PVC,rubber, synthetic wood pulp (SWP), glass fibers, cellulosic fibers, orcombinations thereof, more preferably a microporous membrane made fromthermoplastic polymers. The possibly preferred microporous membranes mayhave pore diameters of about 0.1 micron (100 nanometers) and porositiesof about 60%. The thermoplastic polymers may, in principle, include allacid-resistant thermoplastic materials suitable for use in lead acidbatteries. The preferred thermoplastic polymers include polyvinyls andpolyolefins. The polyvinyls include, for example, polyvinyl chloride(PVC). The polyolefins include, for example, polyethylene, ultrahighmolecular weight polyethylene (UHMWPE), and polypropylene. One preferredembodiment may include a mixture of filler (for example, silica and/orreactive mineral) and UHMWPE. In general, the preferred separatorprecursor may be made by mixing, in an extruder, about 30% by weightfiller with about 10% by weight UHMWPE, and about 60% processing oil.The mixture may also include minor amounts of other additives or agentsas is common in the separator arts (such as wetting agents, colorants,antistatic additives, and/or the like) and is extruded into the shape ofa flat sheet. The ribs are preferably formed by the engraved surfaces ofopposed calender rollers. Thereafter, much of the processing oil isextracted, and the microporous membrane is formed.

With reference again to FIGS. 5 and 26 of the drawings, in accordancewith one particular example, the negative cross ribs are about 4 milsthick, the backweb is about 6 mils thick and the positive ribs are about20 mils thick (total separator thickness about 30 mils). The preferredseparator may be a cut piece or leaf separator (of FIG. 33) or awrapping, envelope, pouch, pocket, with or without an optional laminate(see FIG. 27), glassmat (of FIG. 33), or synthetic non-woven, and mayhave minor transverse cross-ribs on the opposite face of the separatoras the major longitudinal ribs.

The transverse cross-ribs on the opposite face of the separator as thelongitudinal ribs increase stiffness and protection of the sheetallowing for reduction of mass of the back-web, reduced ER, reducedcost, and increased physical properties such as may be required for highspeed production and assembly (including high speed separator, envelope,and/or battery production and/or assembly). Such separators orprecursors can be produced in rolls, envelopes (or pockets) and pieces,and may be used where processing of separators by high speed automationor hand assembly is utilized and high productivity is desired.

Also, the mass of the separator can be reduced while maintainingphysical properties needed for processing and performance inside thebattery by adding transverse or cross ribs opposite, for example, themajor longitudinal ribs. The mass of the major rib is preferably reducedwhen the cross ribs are added to the opposite side to achieve thedesired overall separator thickness (major rib+backweb+cross rib). Thesheet can also be reduced in thickness and/or mass while maintainingproductivity properties such as rigidity as well as protecting the sheetfrom abrasion and oxidation rips and tears during the life of thebattery by adding transverse or cross ribs.

In accordance with at least one example or embodiment, small, tightlyspaced transverse ribs are added to the side of the lead acid separatorwhich contacts the negative electrode (preferably in addition to majorribs on the positive side). The small, tightly spaced negativetransverse ribs can be in many different forms, including withoutlimitation, sinusoidal, diagonal or straight rib patterns, that arecontinuous or discontinuous. For ease of processing, rounded straightribs may be preferred.

The positive longitudinal major ribs can take many forms that runsubstantially in the longitudinal directional, for example, sinusoidal,diagonal or straight ribs, which are continuous or discontinuous. Forease of processing, rounded straight ribs may be preferred. In certainbattery designs, often referred as the Japanese Design, there are nopositive ribs, instead they are replaced with a heavy glass-matlaminated to the flat positive face of the separator. In this glass-matpositive face separator embodiment, the transverse negative ribs of thepresent invention function in the same fashion as the embodiments withpositive longitudinal ribs. The positive face may be smooth or flat,have projections, have ribs, or have a nonwoven bonded or laminatedthereto. Such nonwoven materials may be formed of synthetic, natural,organic or inorganic materials or blends, such as fiberglass, polyester(PET), recycled PET, or combinations thereof (with or without theinventive reactive minerals). The separator may be a cut piece separatoror a wrap, envelope, pouch, or pocket type separator.

With regard to at least selected particular embodiments or examples ofseparators, the preferred separator has the following:

-   1) Transverse Rib Height—preferably between about 0.02 to 0.30 mm,    and most preferably between about 0.075 to 0.15 mm.-   2) Sheet (Substrate) Thickness—preferably between about 0.065 to    0.75 mm.-   3) Overall Thickness (positive rib+backweb+negative rib)—overall    thickness of the separator preferably between about 0.200 to 4.0 mm.-   4) Mass Reduction—preferably greater than 5%, more preferably    greater than 10%. The transverse ribs increase the transverse    rigidity of the separator and allow for the backweb or substrate    thickness to be decreased. Mass can be removed from both the backweb    and positive ribs while maintaining and increasing the transverse    rigidity. Also, the transverse negative ribs contribute to overall    thickness of the separator. Therefore the height of the longitudinal    positive rib can be directly reduced by the height of the negative    cross rib.-   5) Type of Separator—the separator can be made of porous materials,    such as microporous or macroporous thermoplastic material,    preferably polyethylene, polypropylene, polyvinyl chloride, and the    mixtures thereof, as well as of rubber, polyolefin, phenolic,    crosslinked phenolic resin, cellulosic, glass, or combinations    thereof.

Additional or alternative benefits of the addition of negative crossribs include:

-   1) Electrical Resistance Reduction—Since the negative cross rib    profile design allows for mass removal while maintaining equivalent    or higher transverse bending stiffness, the observed electrical    resistance will preferably be lower.-   2) Minimize Tear Propagation—When the separator is extremely    oxidized, a crack or split will likely develop in the backweb and    extend parallel to the major longitudinal rib. The negative cross    rib will preferably arrest the propagation of such tears due to, for    example, the extra mass in the ribs.-   3) Side Alignment—In the assembly process, the enveloped plates are    aligned horizontally and vertically before the strap is cast to    connect the positive and negative electrodes respectively. For    vertical alignment, the positive ribs provide a means for the    separator and plate to slide when contacting each other. For typical    side alignment, the negative plate may slide when contacting the    flat backweb. The negative transverse ribs, will preferably offer    less surface and should aid in side alignment operation.

In accordance with at least one embodiment, the separator is made up ofan ultrahigh molecular weight polyethylene (UHMWPE) mixed with aprocessing oil and filler of precipitated silica and/or reactivemineral. In accordance with at least one particular embodiment, thenegative cross ribs preferably have a 2 to 6 mil radius and a 10 to 50mil rib spacing.

In accordance with at least selected embodiments, the battery separatorincludes a porous membrane having a backweb and at least two rows ofpositive ribs on the positive side of the backweb, and a plurality ofnegative cross ribs or transverse ribs on the negative side of thebackweb. The positive ribs may be straight or wavy, may have a solidportion, and may have a truncated pyramidal shape. The membrane may beselected from the group of polyolefin, rubber, polyvinyl chloride,phenolic, cellulosic, or combinations thereof, and the membrane ispreferably a polyolefin material forming a battery separator for astorage battery.

A battery separator is used to separate the battery's positive andnegative electrodes, and is typically microporous so that ions may passthere through to the positive and negative electrodes. In lead/acidstorage batteries, either automotive or industrial batteries, thebattery separator is typically a microporous polyethylene separatorhaving a back web and a plurality of positive ribs standing on the backweb. The separators for automotive batteries are typically made incontinuous lengths and rolled, subsequently folded, and sealed along itsedges to form pouches that receive the electrodes for the batteries. Theseparators for industrial (traction) batteries are typically cut to asize about the same as an electrode plate (piece separator).

In one embodiment of the present method of making a lead/acid batteryseparator from a sheet of plastic material, the sheet is calender moldedto form cross or negative side transverse ribs or projections, andpreferably is calender molded to simultaneously form both positivelongitudinal ribs and negative cross or transverse ribs on oppositesides of the sheet.

Once a battery is sufficiently charged and current is continuallyapplied (i.e., overcharging), hydrogen is generated at the negativeplate, and oxygen is generated at the positive plate. As hydrogen isformed at the negative plate, it may push the separator away from thenegative plate thereby forming a gas pocket which may prevent the escapeof gas. At least selected embodiments of the present invention mayaddress this issue and provide an improved battery separator. Forexample, the negative cross ribs extending across the back or negativesurface may be interrupted by flat areas, fissures or recesses behindeach positive rib (see FIG. 26). The flats, fissures or recesses mayform channels which may extend longitudinally and may provide for theescape of hydrogen gas, may allow for extraction of plasticizer orlubricant from the positive ribs, and/or the like. A separator havingsuch channels that allow any hydrogen gas to escape may be preferred.

In at least one embodiment, the separator is made of a microporous,thermoplastic material which is provided with longitudinal positive ribsand transverse negative ribs with the height of at least a majority ofthe longitudinal ribs being greater than that of the transverse ribs,and the longitudinal and transverse ribs being solid ribs which areformed integrally from the plastic, characterized in that the transverseribs extend across substantially the entire back width of the separator.The separator sheet thickness may be approximately 0.10 to 0.50 mm, theheight of the longitudinal ribs may be 0.3 to 2.0 mm and the height ofthe transverse ribs may be 0.1 to 0.7 mm, the longitudinal rigidity with100 mm width may be approximately 5 mJ and the transverse rigidity maybe approximately 2.5 mJ, and the total thickness of the separator may beless than 2.5 mm.

The separators according to the present invention can be manufactured ina similar fashion as conventional polyethylene separators with theaddition or substitution of reactive mineral fillers, a negative rollhaving grooves to form the negative cross ribs, a positive roll havingno grooves or grooves of less depth, and/or the like. In a preferredmethod, the plastic material containing filler is extruded through aslot die to form a film and then run through two calender rolls(positive roll, negative roll) by means of which both the positivelongitudinal ribs and the negative transverse ribs are produced and theseparator sheet is reduced to the desired thickness. The positive rollmay have shallow circumferential or annular grooves which form thepositive longitudinal ribs and lands or smooth areas or stripes thatform smooth areas on the separator for sealing the edges of the pockets.The negative roll may have shallow axial grooves which form the crossribs. Also, the negative roll may have spaced sets of shallow axialgrooves with smooth lands or areas (for example, for welding zones)there between.

The separators according to the present invention with negative crossribs preferably have a better machine workability than those withoutsuch transverse ribs, a better guidance of the separator tracks as aresult of increased transverse rigidity, and the processability forplacing the electrode plates in pockets should be improved because ofthe increased transverse rigidity. In addition, production of separatorswith a considerably reduced sheet thickness and consequently with areduced electrical resistance should be possible which is ofsignificance particularly in relation to efforts to constantly increasebattery output with a constant battery volume. The separators accordingto the invention should be able to be processed to form pockets withoutdifficulty on conventional machines. The additional transverse negativeribs should not cause problems either with the welding of the pockets bythe use of heat or ultrasonic means or with the mechanical process forproducing pockets.

In at least one particular embodiment, the separator made of elasticplastic and suitable for use in a lead acid storage battery, includessheet material with an inner region and two peripheral regions andhaving positive ribs running in the longitudinal direction with thelongitudinal ribs in the inner region being more widely spaced thanthose in the peripheral region, and having negative ribs running in thetransverse direction.

A new or improved lead acid battery may preferably include: a housingcontaining a positive electrode spaced apart from a negative electrodewith a porous separator located between the positive electrode and thenegative electrode and an electrolyte in ionic communication between thepositive electrode and the negative electrode, and at least one of thehousing, separator, positive electrode, negative electrode, andelectrolyte include at least one natural or synthetic hydroxyapatitemineral.

A new or improved lead acid battery may preferably include: a housingcontaining a positive electrode spaced apart from a negative electrodewith a porous separator located between the positive electrode and thenegative electrode and an electrolyte in ionic communication between thepositive electrode and the negative electrode, and at least two of thehousing, separator, positive electrode, negative electrode, andelectrolyte include at least one natural or synthetic hydroxyapatitemineral.

A new or improved lead acid battery may preferably include: a housingcontaining a positive electrode spaced apart from a negative electrodewith a porous separator located between the positive electrode and thenegative electrode and an electrolyte in ionic communication between thepositive electrode and the negative electrode, and at least three of thehousing, separator, positive electrode, negative electrode, andelectrolyte include at least one natural or synthetic hydroxyapatitemineral.

A new or improved lead acid battery may preferably include: a housingcontaining a positive electrode spaced apart from a negative electrodewith a porous separator located between the positive electrode and thenegative electrode and an electrolyte in ionic communication between thepositive electrode and the negative electrode, and at least four of thehousing, separator, positive electrode, negative electrode, andelectrolyte include at least one natural or synthetic hydroxyapatitemineral.

A new or improved lead acid battery may preferably include: a housingcontaining a positive electrode spaced apart from a negative electrodewith a porous separator located between the positive electrode and thenegative electrode and an electrolyte in ionic communication between thepositive electrode and the negative electrode, and each of housing,separator, positive electrode, negative electrode, and electrolyteinclude at least one natural or synthetic hydroxyapatite mineral.

The new or improved separators of the present invention may find use asLead-Acid Battery Separators, separators for use in starting,deep-cycling and stand-by power battery applications, or in Flooded, Geland AGM battery types used in applications such as: starting,stationary, motive power and deep-cycle lead-acid battery applications,as well as for flooded and specialty lead-acid battery applications,and/or for premium lead-acid gel batteries. Further, such separators maybe used in other batteries, accumulators, capacitors, and/or the like.

In accordance with at least certain embodiments, it is preferred that atleast one source of hydroxyapatite mineral (such as ground fish meal) beadded to substitute for a portion of the silica filler in a silicafilled separator at substitution levels of about 1% to 50% of thesilica, more preferably about 5% to 30%, and most preferably at about10% to 20%.

In accordance with at least other certain embodiments, it is preferredthat at least one source of hydroxyapatite (such as ground fish meal) beadded as the filler in a filled separator at filler levels of about 1%to 75% filler, more preferably about 5% to 50%, and most preferably atabout 10% to 30%.

In accordance with at least still other certain embodiments, it ispreferred that at least one source of hydroxyapatite (such as groundfish meal) be added as filler in a battery separator at levels of about1% to 75% weight percent of the separator, more preferably about 2% to35%, and most preferably at about 5% to 20%.

In accordance with at least selected embodiments of the presentinvention, a believed novel concept of utilizing PIMS minerals as afiller component within a microporous lead-acid battery separator isprovided. In accordance with one particular embodiment or example, thePIMS mineral (preferably fish meal, a bio-mineral) is provided as atleast a partial substitution for the silica filler component in a silicafilled lead acid battery separator (preferably a polyethylene/silicaseparator formulation).

In accordance with at least certain embodiments of the presentinvention, a novel concept of utilizing one or more natural or syntheticPIMS minerals as a filler component within a microporous lead-acidbattery separator is provided. In accordance with more particularembodiments or examples, a PIMS mineral (preferably fish meal, abio-mineral) is provided as at least a partial substitution for thesilica filler component in a silica filled lead acid battery separator(preferably a polyethylene/silica separator formulation). In accordancewith at least selected embodiments, the present invention is directed tonew or improved batteries, separators, components, and/or compositionshaving heavy metal removal capabilities and/or methods of manufactureand/or methods of use thereof.

In accordance with at least selected embodiments of the presentinvention, a believed novel concept of utilizing PIMS minerals as afiller component within a microporous PE ISS lead-acid battery separatoris provided. In accordance with one particular embodiment or example,the PIMS mineral (preferably fish meal, a bio-mineral) is provided as atleast a partial substitution for the silica filler component in a silicafilled lead acid battery separator (preferably a polyethylene/silicaseparator formulation).

A common failure mode within the lead-acid battery industry is thephenomenon of “hydration shorts”. The conventional approach to theprevention of hydration shorts consists of addition of Sodium Sulfate(Na2SO4) to the electrolyte solution during battery manufacture. Thisapproach requires an additional manufacturing step, adding complexity tothe battery processing. Sodium Sulfate addition acts to “hinder”hydration shorts.

In accordance with the present invention, a variety of PIMS mineralshave been identified; some of which have been evaluated for leadaffinity. A PIMS mineral derived from fish bone (such as commercial, labground fish meal) has been shown to have greatest affinity for lead ionover the other natural or synthetic samples evaluated.

In accordance with at least selected embodiments, lead reduction isachieved by incorporating PIMS minerals in ISS lead-acid batteryseparators, preferably incorporating PIMS mineral derived from fishbone.

In accordance with at least selected embodiments of the presentinvention, a believed novel concept of utilizing PIMS minerals as afiller component within a microporous ISS lead-acid battery separator isprovided. In accordance with one particular embodiment or example, thePIMS mineral (preferably fish meal, a bio-mineral) is provided as atleast a partial substitution for the silica filler component incontemporary silica filled lead acid battery separator (preferably apolyethylene/silica separator formulation).

In accordance with at least selected embodiments or objects of thepresent invention, there are provided:

An ISS battery separator having at least one of negative cross ribs, asilica to polymer ratio greater than 3:1, and one or more PIMS mineralsas a filler component.

The above ISS battery separator, having one or more fish bone or fishmeal fillers.

The above ISS battery separator, wherein the separator is a silicafilled polyethylene battery separator having the fish bone or fish mealfiller substituted for at least a portion of the silica filler.

In a flooded lead acid battery, the improvement comprising the above ISSbattery separator.

In an ISS electrical system, the improvement comprising the abovebattery.

An ISS battery separator having multiple separator properties of chargeacceptance, power delivery, reduced hydration shorts, improved cyclelife, and reduced acid stratification optimized simultaneously.

In an ISS lead acid battery, the improvement comprising the aboveseparator.

In an ISS vehicle, the improvement comprising the above battery.

A battery separator comprising at least three of the followingimprovements, features, changes, modifications, enhancements,performance, characteristics, profiles, shapes, configurations,structures, parts, attributes, spacing, thicknesses, ratios, blends,mixtures, formulations, additives, agents, coatings, layers, laminates,mats, non-wovens, surfaces, inclusions, effects, embodiments, orexamples:

-   -   1) Charge Acceptance/Power Delivery—features of or changes to        the separator to help increase charge acceptance/power delivery:        -   a. Low or Lower Electrical Resistance (ER)—minimization of            separator ER, via the following methods:            -   i. Lower Back-Web (BW) Thickness—reduce the BW thickness                from typical values which range from 150 to 250 micron                by lowering the BW thickness between 75 to 150 microns                and then reinforcing the transversal stiffness with the                use of negative cross ribs,            -   ii. Increase Silica to Polymer Ratio—increase the                loading of silica, relative to the polymer content, have                a silica to polymer ratio from about 3.0/1.0 to 5.0/1.0,            -   iii. Utilize High Oil Absorption (High Surface Area)                Silica (Increase Porosity)—include a silica with a high                surface area (e.g. >200 g/m2), which typically yields a                high oil absorption, an amount of pore forming agent                from about 70 to 80% by weight in the extrusion process,        -   b. Minimize Gas Entrapment—reduce opportunity for gas            entrapment:            -   i. Laminate Structure and Modifications—modified                laminate structure to reduce gas entrapment,                -   1. Treatment of the laminate with a chemical or                    plasma to modify surface energy to shed gas bubbles,                -   2. Perforation to allow bubbles an area to coagulate                    and escape the laminate matrix,                -   3. Addition of nucleating agents,                -   4. Changing the structure of the laminate during                    formation,                -   5. Addition of polymer fibers and/or shaped polymer                    fibers to the laminate structure,                -   6. Addition of wetting agents (or surfactants),                -   7. Change the orientation on the fiber structure of                    the laminate so gas bubbles are less likely to                    attach to the structure,                -   8. Minimize the thickness of the structure so that                    there are simply less sites for bubble adhesion,            -   ii. Wetting Agent Selection—use a more hydrophobic                wetting agent, use an ethoxylated fatty alcohol,            -   iii. Separator Cross-Ribs (Negative and/or                Positive)—have small negative cross ribs to assist in                the nucleation or transport of gas bubbles or to allow                the gas to escape from between the plates, or reducing                the potential for gas entrapment,            -   iv. Nucleation of Gas—have areas on the separator to act                as nucleation sites for gas bubbles to quickly and                efficiently grow to the point where they are released                from the separator and travel out of the area between                the plates,                -   1. Profile Shape (Roughness)—add nanostructures on                    the surface of the separator to increase gas                    nucleation, such nanostructures may take the form of                    pyramids, chevrons, or pillars, and may be formed by                    calendaring, laser ablation or controlled chemical                    oxidation,                -   2. Additives—have additives incorporated into the                    matrix of the separator (or on the surface) in order                    to provide areas on the surface where they change                    the surface structure or energy to encourage the                    nucleation of small gas bubbles generated to a                    critical volume, the additives may be carbon fibers,                    carbon nanotubes, or barium sulfate,    -   2) Hydration Shorts (Hinder, Delay, Reduce, Eliminate)—add        sodium sulfate to the electrolyte to hinder hydration shorts, or        -   a. Common Ion Effect—have sodium sulfate incorporated into            the separator matrix and/or laminate materials (such as by            impregnation),        -   b. Heavy Metal Sequestration—sequester lead ions that are in            solution by incorporating apatite, hydroxyapatite minerals,            ground fish meal, zeolites, lignins, latex, or            rubber-derivatives into the separator (or on the separator            surface, in the laminate material, in the electrolyte, in            the battery casing, and/or the like) to inhibit hydration            short formation,        -   c. Location of Additives—have additives in the matrix of the            separator (preferably as a substitution filler for part of            the silica), coated on the separator, coated on or contained            in the laminate structure, coated onto the container of the            battery case either before or after the injection molding            process, or placed in porous bags or sachets in the            electrolyte or laminate structure,        -   d. Lower or Reduced Acid Displacement—via separator            modifications including:            -   i. Thin Backweb—lower the backweb (BW) thickness with                added cross ribs (preferably negative cross ribs as                discussed above), higher porosity, or less rib mass of                the separator,            -   ii. Serrated/Battlement Ribs—use serrated or battlement                rib design to remove mass from the ribs,    -   3) Improve Cycle Life—by modifying the separator as follows:        -   a. Laminate Structure—utilize a laminate to retain the            positive active mass in the positive grid,            -   i. Glass Mat—utilize glass mats having different fiber                lengths and widths in the mats ranging in compressed                thickness from 0.1 mm to 1.0 mm,            -   ii. Synthetic Nonwovens—utilize nonwoven polymeric mats,                polyester mats,            -   iii. Hybrid—utilize a hybrid mat of glass fibers mixed                with polymer fibers,        -   b. Profile Selection—contribute to lower acid displacement            by profile design selection, use a profile having tight rib            spacing with shorter rib height, narrower ribs, or            battlement ribs,        -   c. Polyaspartic Acid—add polyaspartic acid directly to the            matrix of the separator, or as coated on the separator,            coated on or contained in the laminate structure, coated            onto the container of the battery case either before or            after the injection molding process, placed in porous bags            or sachets in the electrolyte or laminate structure,        -   d. Compression—use a compressible, flexible or resilient rib            structure to enhance cycle life, such as an I-beam rib            profile,    -   4) Acid Stratification—overcharge the battery to some degree        promote the electrolysis of water, or        -   a. Profile Selection—incorporate horizontal ribs across the            surface of the separator,        -   b. Laminate Structure—add a laminate structure attached to            the polyethylene separator, align the fibers in a certain            pattern across and through the material, add a laminate            structure to both the positive and negative face of the            polyethylene separator,        -   c. Surface Area—increase the surface area of the separator            structure, decrease the fiber diameter of the laminate            structure, or increase the internal surface of the separator            by the type or concentration of silica, adding porosity,            having cross ribs,        -   d. Acid Immobilization—immobilize the acid by having cross            ribs which tend to hold the acid in place, adding a silica            layer on the laminate and/or separator surface or adding            silica in the laminate to “gel” the acid, or utilizing            Daramic AJS technology,        -   e. Polyethylene/Absorptive Glass Mat Hybrid—incorporate a            flat PE separator membrane into or on one side of an AGM            separator, and        -   f. Other Laminate Hybrids—utilize other laminate systems,            whether nonwovens or other glass mats in conjunction with a            flat PE separator membrane to make an acceptable separator.

The above separator, having negative cross ribs.

In a lead acid battery, the improvement comprising the above separator.

A battery separator, such as a deep cycle, ISS or micro-hybridseparator, comprising at least two of the following: features that helpminimize acid stratification, that occupies approximately 15% lessvolume than traditional separators, has negative cross ribs, has amultitude of small mini-ribs in the horizontal direction, has amechanical barrier that will hinder an acid gradient from developing,has hundreds of mini dams to keep heavier acid from flowing downward,has hundreds of mini dams which create hundreds of mini pools of aciduniformly across the surface of the electrode, and that improves powerdelivery and reduces acid stratification in micro-hybrid batteries.

In a method of producing a silica filled battery separator, theimprovement comprising: substituting at least one PIMS mineral for atleast a portion of the silica filler.

In a lead acid battery, the improvement comprising at least one of: aseparator, component, or composition having heavy metal removalcapabilities utilizing at least one PIMS mineral; a battery casing,battery part, porous bag, laminate, non-woven, mat, paper, coating,surface, in-mold, filler, electrode, electrode formulation, electrolyte,polymer composition, or resin composition having heavy metal removalcapabilities utilizing at least one PIMS mineral; a polymer or resincomposition having heavy metal removal capabilities utilizing at leastone PIMS mineral as at least one filler component therein; a silicafilled microporous lead-acid battery separator having at least one PIMSmineral provided as at least a partial substitution for the silicafiller therein; a silica filled microporous polyethylene lead-acidbattery separator having ground fish meal provided as at least a partialsubstitution for the silica filler therein; or combinations thereof.

The present invention may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.

1-14. (canceled)
 15. A membrane for an acid-containing battery, whereinthe membrane is a polymeric filled porous flat-sheet membrane.
 16. Themembrane of claim 15, wherein the membrane is a filled microporouspolyolefin flat-sheet membrane.
 17. The membrane of claim 15, whereinthe membrane is a polymeric filled macroporous flat-sheet membrane,wherein the polymer is one or more selected from rubber, PVC, syntheticwood pulp (SWP), glass fibers, cellulosic fibers, polypropylene, andcombinations thereof.
 18. The membrane of claim 16, comprisingpolyolefin, silica, and oil.
 19. The membrane of claim 18, wherein thesilica has a surface area greater than 200g/m2.
 20. The membrane ofclaim 18, wherein the silica to polymer ratio is from 3.0/1.0 to5.0/1.0.
 21. The membrane of claim 20, wherein the silica to polymerratio is from 3.0/1.0 to 4.0/1.0.
 22. The membrane of claim 15, havingan overall thickness of 0.200 mm to 4.0 mm.
 23. The membrane of claim15, comprising a material having heavy metal removal capabilities. 24.The membrane of claim 23, wherein the material is one or more selectedfrom an apatite mineral, a hydroxyapatite mineral, ground fish meal,zeolites, lignins, latex, and rubber-derivatives.
 25. The membrane ofclaim 24, wherein the material is latex.
 26. The membrane of claim 24,wherein the material is a rubber-derivative.
 27. The membrane of claim15, comprising nucleation additives in or on a surface of the membrane.28. The membrane of claim 27, wherein the nucleation additives compriseone or more selected from carbon fiber, carbon nanotubes and bariumsulfate.
 29. The membrane of claim 15, wherein the polymer ispolyethylene and the membrane further comprises a wetting agent.
 30. Themembrane of claim 29, wherein the wetting agent is hydrophobic.
 31. Themembrane of claim 30, wherein the wetting agent is an ethoxylated fattyalcohol.
 32. The membrane of claim 15, comprising one or more of thefollowing properties: an average pore size of 0.1 microns; a maximumpore size <1 microns; an Electrical Resistance less than 0.065 (Ohm cmsq); and a porosity of 60% to 80%.
 33. The membrane of claim 32 havingat least two of the properties.
 34. The membrane of claim 32, having atleast three of the properties.